PAPER
Synthesis of Thioureas and Thiuram Disulfides
3583
Anal. Calcd for C7H5NOS: C, 55.61; H, 3.33; N, 9.26. Found: C,
55.54; H, 3.37; N, 9.30.
Dipentamethylenethiuram Disulfide (4e)
White solid; mp 124–126 °C.
IR (KBr): 2939, 2854, 1653, 1636, 1558, 1506, 1479, 1454, 1429,
1362, 1281, 1257, 1242, 1221, 1137, 1107, 1019, 1005, 958, 892,
852, 599, 512, 458, 418 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.76 (s, 12 H), 4.22 (m, 8 H).
13C NMR (125 MHz, CDCl3): d = 192.91, 56.10, 52.87, 26.74,
25.72, 24.46.
Tetramethylthiuram Disulfide (4a); Typical Procedure
CS2 (0.12 mL, 1.0 mmol) was added to a soln of 3a (0.30 mL, 2.0
mmol) in DMF (2.0 mL) in an ice-water bath and the mixture was
stirred for 5 min. CBr4 (331 mg, 1.0 mmol) was added and the mix-
ture was stirred at r.t. for 0.5 h and then poured into ice-water (80
mL) with stirring. The mixture was extracted with CH2Cl2 (3 × 60
mL). The combined organic layers were concentrated and subjected
to column chromatography (silica gel, petroleum ether–EtOAc, 10:
1) to give 4a (228 mg, 95%) as a white solid; mp 154–156 °C.
MS: m/z [M]+ calcd: 320.0; found: 321.0 [M + 1]+.
Anal. Calcd for C12H20N2S4: C, 44.96; H, 6.29; N, 8.74. Found: C,
45.21; H, 6.28; N, 8.77.
IR (KBr): 2931, 2785, 1506, 1458, 1400, 1375, 1236, 1149, 970,
849 cm–1.
1H NMR (500 MHz, CDCl3): d = 3.60 (s, 6 H), 3.63 (s, 6 H).
13C NMR (125 MHz, CDCl3): d = 193.92, 47.82, 42.31.
MS: m/z [M]+ calcd: 240.0; found: 241.0 [M + 1]+.
Diisopropyl Xanthogen Disulfide (5)
Na (0.046 g, 2.0 mmol) was added to anhyd i-PrOH (2 mL) in an
ice-water bath. After the Na had dissolved, CS2 (0.12 mL, 2.0
mmol) was then added followed by CBr4 (331 mg, 1.0 mmol). The
mixture was stirred at r.t. for 1.0 h and then poured into ice water
(80 mL) with stirring. The mixture was extracted with CH2Cl2 (3 ×
60 mL) and the combined organic layers were concentrated and
subjected to column chromatography (silica gel, petroleum ether–
EtOAc, 24:1) to give 5 (137 mg, 51%) as a yellow solid; mp 52–54
°C.
Anal. Calcd for C6H12N2S4: C, 29.97; H, 5.03; N, 11.65. Found: C,
30.11; H, 5.01; N, 11.62.
Tetraethylthiuram Disulfide (4b)
White solid; mp 70–72 °C.
IR (KBr): 2974, 2915, 2869, 1506, 1497, 1457, 1418, 1375, 1350,
1272, 1195, 1149, 1060, 966, 912, 817, 669 cm–1.
IR (KBr): 2981, 2930, 1693, 1378, 1265, 1087, 1007, 897, 796
cm–1.
1H NMR (500 MHz, CDCl3): d = 1.30 (t, J = 6.5 Hz, 6 H), 1.48 (t,
J = 6.5 Hz, 6 H), 4.02 (q, J = 7.0, 7.5 Hz, 8 H).
1H NMR (500 MHz, CDCl3): d = 1.39 (s, 6 H), 1.40 (s, 6 H), 5.69
(m, 2 H).
13C NMR (125 MHz, CDCl3): d = 192.91, 52.28, 47.84, 13.72,
11.70.
13C NMR (125 MHz, CDCl3): d = 206.7 (2 C), 80.3 (2 C), 21.1 (4
C).
MS: m/z [M]+ calcd: 296.1; found: 297.0 [M + 1]+.
MS: m/z [M]+ calcd: 270.0; found: 271.0 [M + 1]+.
Anal. Calcd for C10H20N2S4: C, 40.50; H, 6.80; N, 9.45. Found: C,
40.34; H, 6.81; N, 9.48.
Anal. Calcd for C8H14O2S4: C, 35.53; H, 5.22. Found: C, 35.39; H,
5.19.
Tetrabutylthiuram Disulfide (4c)
Yellow liquid.
Acknowledgment
IR (KBr): 2958, 2930, 2871, 1488, 1457, 1416, 1367, 1291, 1248,
1221, 1179, 1146, 1091, 1111, 1002, 935, 905, 863, 733, 669, 418
cm–1.
Financial support of this research by NSFC (20672019), NENU-
STB07007 and Science Foundation for Young Teachers of Nort-
heast Normal University (20060313) is gratefully appreciated.
1H NMR (500 MHz, CDCl3): d = 0.93 (t, J = 7.0, 7.5 Hz, 6 H), 1.00
(t, J = 7.0, 7.5 Hz, 6 H), 1.33 (q, J = 7.0, 7.5 Hz, 4 H), 1.44 (q, J =
7.5 Hz, 4 H), 1.72 (m, 4 H), 1.88 (m, 4 H), 3.93 (m, 8 H).
References
13C NMR (125 MHz, CDCl3): d = 190.68, 55.18, 50.99, 27.97,
(1) (a) Hunter, W. H.; Edgar, D. E. J. Am. Chem. Soc. 1932, 54,
2025. (b) Abele, E.; Rubina, K.; Abele, R.; Gaukhman, A.;
Lukevics, E. J. Chem. Res., Synop. 1998, 618. (c)Abele,E.;
Fleisher, M.; Rubina, K.; Abele, R.; Lukevics, E. J. Mol.
Catal. A: Chem. 2001, 165, 121. (d) Schreiner, P. R.;
Lauenstein, O.; Kolomitsyn, I. V.; Nadi, S.; Fokin, A. A.
Angew. Chem. Int. Ed. 1998, 37, 1895. (e) Fokin, A. A.;
Schreiner, P. R. Adv. Synth. Catal. 2003, 345, 1035.
(f) Camps, X.; Schönberger, H.; Hirsch, A. Chem. Eur. J.
1997, 3, 561.
25.89, 17.83, 17.79, 11.52, 11.47.
MS: m/z [M]+ calcd: 408.2; found: 409.0 [M + 1]+.
Anal. Calcd for C18H36N2S4: C, 52.89; H, 8.88; N, 6.85. Found: C,
53.01; H, 8.90; N, 6.84.
Bis(3-oxapentamethylene)thiuram Disulfide (4d)
White solid; mp 120–122 °C.
IR (KBr): 2961, 2916, 2853, 1739, 1688, 1645, 1514, 1473, 1419,
1300, 1263, 1227, 1110, 1061, 1030, 977, 908, 858, 797, 674, 533
cm–1.
1H NMR (500 MHz, CDCl3): d = 3.84 (t, J = 5.0 Hz, 8 H), 4.30 (s,
8 H).
13C NMR (125 MHz, CDCl3): d = 194.07, 66.65, 54.14, 52.00.
MS: m/z [M]+ calcd: 324.0; found: 325.0 [M + 1]+.
(2) Kharasch, M. S.; Jensen, E. V.; Urry, W. H. J. Am. Chem.
Soc. 1946, 68, 154.
(3) (a) Yadav, J. S.; Reddy, B. V. S.; Harikishan, K.; Madan, C.;
Narsaiah, A. V. Synthesis 2005, 2897. (b) Chandra, T.;
Brown, K. L. Tetrahedron Lett. 2005, 46, 8617. (c) Chen,
M.-Y.; Patkar, L. N.; Jan, M.-D.; Lee, A. S.-Y.; Lin, C.-C.
Tetrahedron Lett. 2004, 45, 635. (d) Chen, M.-Y.; Lee, A.
S.-Y. J. Org. Chem. 2002, 67, 1384.
(4) (a) Appel, R. Angew. Chem., Int. Ed. Engl. 1975, 14, 801.
(b) Rabinowitz, R.; Marcus, R. J. Am. Chem. Soc. 1962, 84,
1312.
Anal. Calcd for C10H16N2O2S4: C, 37.01; H, 4.97; N, 8.63. Found:
C, 37.28; H, 4.99; N, 8.65.
Synthesis 2008, No. 22, 3579–3584 © Thieme Stuttgart · New York