D. Onyancha et al. / Journal of Organometallic Chemistry 694 (2009) 207–212
211
minutes (ꢂ5–10 min), a paste was formed, and in some cases it
solidified after further grinding. The progress of the reaction was
monitored by TLC, and in most cases it was complete within an
hour. However, some reactions took longer (ꢂ3 h) before maxi-
mum conversion was obtained. After grinding for 3 h, the resulting
residue was dissolved in dichloromethane. The reaction mixture
was then purified by column chromatography using silica gel. Elu-
tion with hexane/ether (1:1) and removal of the solvent and drying
under vacuo provided the product S,S-bis(ferrocenylmethyl)
dithiocarbonate.
b. Solvent conditions. Ferrocenylmethanol (1a) (200 mg,
0.93 mmol) and TCDI (170 mg, 0.95 mmol) were added to anhy-
drous dichloromethane (50 cm3) and heated under reflux for 3 h
under nitrogen. The reaction mixture was then concentrated and
purified by column chromatography using silica gel. Elution with
hexane/ether (1:1) and removal of the solvent and drying under
vacuo provided the product S,S-bis(ferrocenylmethyl)dithio-
carbonate.
3.1.3.2. O-(6-Ferrocenylhexyl)-1H-imidazole-1-carbothioate (3d). 6-
Ferrocenylhexan-1-ol (3b) (310 mg, 1.10 mmol) and N,N0-thi-
ocarbonyldiimidazole (360 mg, 1.30 mmol). The product was
isolated as a yellow oil (410 mg, 96%), (341 mg, 80%*); IR (NaCl,
cmꢀ1): 3092, 2931, 2855, 1762, 1709, 1530, 1461, 1385, 1329,
1286, 1232, 1105, 1040, 986, 891, 820; 1H NMR (CDCl3): 8.37
(1H, s, ArH) 7.67(1H, s, ArH), 7.08 (1H, s, ArH), 4.66 (2H, t, J, 6.57
C2H2), 4.12 (5H, s, C5H5), 4.08 (4H, 2 ꢁ C5H4), 2.34 (2H, t, J 7.1,
CH2), 1.91 (2H, q, J CH2) 1.46 (6H, m, 3 ꢁ CH2); 13C NMR (CDCl3):
185.58, 139.12, 131.54, 120.08, 89.46, 74.29, 68.87, 68.47, 67. 50,
31.45, 29.94, 29.48, 28.41, 26.24; MS: m/z (EI) 396 (M+, 100%).
3.1.3.3. O,O0-[1,10-Ferrocenyl bis(methylene)] bis(1H-imidazole-1-
carbothioate)
(3f). 1,10-Ferrocenedimethanol
(3e)
(100 mg,
0.46 mmol) and TCDI (200 mg, 1.10 mmol). The product was iso-
lated as a yellow solid (93 mg, 43%), (82 mg, 38%*); m.p. 123–
125 °C; IR (KBr, cmꢀ1): 3097, 2924, 2854, 1694, 1527, 1474,
1403, 1362, 1293, 1217, 1101, 884, 668; 1H NMR (CDCl3): 8.29
(2H, s, C3N2H3), 7.55 (2H, s, 2 ꢁ C3N2H3), 7.17 (2H, s, 2 ꢁ C3N2H3),
4.32 (4H, s, 2 ꢁ CH2), 4.24 (4H, s, 2 ꢁ C5H4), 4.22 (4H, s,
2 ꢁ C5H4); 13C NMR (CDCl3); 166.32, 135.97, 131.45, 116.44, 83.
52, 70.19, 70.08, 31.39; MS: m/z (EI) 466 (M+, 100%).
3.1.1. Product with ferrocenyldithiocarbonate
3.1.1.1. S,S-bis(ferrocenylmethyl)dithiocarbonate (1b). Ferrocenyl-
methanol (1a) (200 mg, 0.93 mmol) and TCDI (170 mg,
0.95 mmol). The product was isolated as a yellow solid (51 mg,
22%), (26 mg, 11%*); m.p. 159–160 °C; IR (KBr, cmꢀ1): 3470, 3108,
2927, 2340, 2361, 1635, 1559, 1539,1104, 999, 879, 852, 864; 1H
NMR (CDCl3): 4.21 (4H, t, J 2.1, 2 ꢁ C5H4), 4.18 (10H, s, 2 ꢁ C5H5),
4.14 (4H, t, J 1.8, 2 ꢁ C5H4), 4.07 (4H, s, 2 ꢁ C2H2); 13C NMR (CDCl3):
189.65, 83.88, 69.24, 69.15, 68.66, 31. 31; MS: m/z (EI) 490 (M+,
3.1.4. Benzylthiocarbonates
3.1.4.1. O,O-Bis[(4-trifluoromethyl)benzyl]thiocarbonate (4b). 4-(Tri-
fluoromethyl)benzyl alcohol (4a) (200 mg, 0.93 mmol) and TCDI
(170 mg, 0.95 mmol). The product was isolated as a white solid
(220 mg, 86%), (192 mg, 75%*); m.p. 75–76 °C; IR (KBr, cmꢀ1):
2951, 2294, 1626,1422, 1391, 1336, 1266, 1251, 1165, 1116,
1069, 1019, 947, 866, 829; 1H NMR (CDCl3): 7.66 (4H, d, J 8.2,
4 ꢁ ArH), 7.50 (4H, d, J, 10.9, 4 ꢁ ArH), 5.57 (4H, s, 2 ꢁ CH2); 13C
NMR (CDCl3): 195.14, 138.73, 131.46, 128.77, 126.04, 122.50,
74.01; MS: m/z (EI) 394 (M+, 100%).
*
38%). represents yield obtained under solvent conditions.
3.1.2. Products with ferrocenyl (alkyl)imidazolides
3.1.2.1.
1-(1-Ferrocenylbutyl)-1H-imidazole (2c). 1-Ferrocenylb-
utan-1-ol (2b) (340 mg, 1.30 mmol) and TCDI (278 mg,
1.56 mmol). The product was isolated as a yellow oil (100 mg,
21%), (110 mg, 23%*); IR (NaCl, cmꢀ1): 3470, 3108, 2927, 2340,
2361, 1635, 1559, 1539, 1104, 999, 879, 852, 864; 1H NMR (CDCl3):
7.61 (1H, s, ArH), 7.09 (1H, s, ArH), 6.97(1H, s, ArH), 4.94 (1H, t, J 6,
CH), 4.21 (2H, t, J 2.1, C5H4), 4.18 (5H, s, C5H5), 4.14 (2H, t, J 1.8,
C5H4), 2.06 (2H, m, CH2), 1.20 (2H, m, CH2), 0.95 (3H, t, J 7.2,
CH3); 13C NMR (CDCl3): 136.76, 129.32, 117.74, 89.88, 68.26,
68.78, 67.30, 57.98, 38.88, 20.00, 14.03; MS: m/z (EI) 308 (M+,
100%).
3.2. X-ray crystallography
X-ray diffraction data for S,S0-bis(ferrocenylmethyl)dithiocar-
bonate (1b) were collected on a Bruker Smart 1K CCD diffractom-
eter with graphite-monochromated Mo
Ka radiation. The
collection method involved -scan of width 0.3°. Data reduction
x
was carried out by the program SAINT +, Version 6.02 [12]. Multi-
scan absorption corrections were made with the program SADABS
[13]. The structure was solved by direct methods using SHELXS-97
[14]. Non-hydrogen atoms were first refined isotropically followed
by anisotropic refinement by full-matrix least-squares calculation
based on F2 using SHELXL-97 [14]. Hydrogen atoms were first located
in the difference map, then positioned geometrically and allowed
to ride on their respective parent atoms. The general purpose crys-
tallographic tool PLATON [15] was used for structure analysis, and
ORTEP3 [16] was used for diagram generation.
3.1.2.2. 1-[Ferrocenyl(phenyl)methyl]-1H-imidazole (2d). 1-Ferroce-
nyl-1-phenylmethanol (2a) (200 mg, 6.50 mmol) and TCDI
(170 mg, 7.80 mmol). The product was isolated as a yellow oil
(51 mg, 22%), (58 mg, 25%*), IR (NaCl, cmꢀ1): 2929, 2856, 1544,
1423, 1225, 1108, 1073, 929. 1H NMR (CDCl3): 7.79 (1H, s, ArH),
7.38 (3H, m, ArH), 7.23 (2H, m, ArH), 7.20 (1H, s, ArH), 6.90 (1H,
s, ArH), 4.00 (9H, m, 2 ꢁ C5H4); 13C NMR (CDCl3): 140.29, 137.15,
129.00, 128.70, 127.79, 119.49, 96.52, 87.08, 69.52, 69.28, 68.82;
MS: m/z (EI) 342 (M+, 100%).
Appendix A. Supplementary material
CCDC 697541 contains the supplementary crystallographic data
for 1b. These data can be obtained free of charge from The Cam-
3.1.3. Products with ferrocenylthiocarbonylimidazolides
3.1.3.1. O-4-Ferrocenylphenyl-1H-imidazole-1-carbothioate (3c). 4-
Ferrocenylphenol (3a) (200 mg, 0.72 mmol) and TCDI (308 mg,
1.7 mmol). The product was isolated as a yellow solid (177 mg,
68%), (156 mg, 60%*) m.p. 128–129 °C; IR (KBr, cmꢀ1): 3154,
2925, 2856, 1637, 1518, 1404, 1403, 1325, 1293, 1238, 1212,
1158, 1040, 957, 885; 1H NMR (d6-acetone): 8.60 (1H, s,
1 ꢁ C3N2H3), 7.90 (1H, s, C3N2H3), 7.70 (2H, d, J 8.0 2 ꢁ ArH), 7.31
(2H, d, J 9.0, 2 ꢁ ArH), 7.12 (1H, s, C3N2H3), 4.85 (2H, s, C5H4),
4.40 (2H, s, C5H4) 4.10 (5H, s, C5H5); 13C NMR (d6-acetone):
184.84, 151.54, 139.26, 137.63, 131.50, 127.42, 122.25, 119.173,
84.37, 69.914, 69.58, 66.95; MS: m/z (EI) 388 (M+, 100%).
References
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1574.
[2] P. Camps, J. Contreras, J. Morral, D. Munoz-Terrero, M. Font-Bardia, X. Solans,
Tetrahedron 55 (1999) 8481.