K. Singh, A. Sharma / Tetrahedron 66 (2010) 3682–3686
3685
60.27; H, 4.10; S, 29.22; N, 6.39%]; Rf (10% EtOAc/hexane) 0.82; vmax
(CHCl3) 1520, 1040, 710, 680 cmꢁ1
dH (300 MHz, CDCl3) 7.22–7.31
(2H, m, ArH), 6.99–7.04 (2H, m, ArH), 6.90–6.99 (2H, m, ArH), 4.89
(1H, t, J 7.2 Hz, meso CH), 3.10 (2H, d, J 7.2 Hz, CNCH2); dC (75 MHz,
CDCl3) 143.9, 126.8, 125.2, 125.0, 117.4, 37.7, 27.1; m/z 242 (Mþ23).
7.11–7.22 (4H, m, ArH), 6.77–6.99 (8H, m, ArH), 4.37 (2H, t, J 7.5 Hz,
meso CH), 2.08 (4H, m, CH2(CH2)2CH2), 1.36 (4H, m, CH2(CH2)2CH2);
dC (100 MHz, CDCl3) 148.7, 126.4, 124.0, 123.6, 41.8, 38.6, 27.3; m/z
415 (Mþ1).
;
4.3.4. 1,1,7,7-Tetra(thiophen-2-yl)heptane (3d). White solid; [found:
C, 64.21; H, 5.83; S, 29.74. C23H24S4 requires C, 64.48; H, 5.60; S,
29.90%]; Rf (5% EtOAc/hexane) 0.44; mp: 75–76 ꢀC (DCM/hexane);
4.2.11. 2-Methyl-1,1-di(thiophen-2-yl)propan-2-ol (2k). Colourless
oil; [found: C, 60.21; H, 5.69; S, 27.12. C12H14OS2 requires C, 60.50;
H, 5.88; S, 26.89%]; Rf (10% EtOAc/hexane) 0.76; vmax (CHCl3) 3600,
vmax (KBr) 2865, 1080, 1035, 840, 710 cmꢁ1
; dH (300 MHz, CDCl3)
1375, 1080, 1050, 1025, 845, 710 cmꢁ1
;
dH (300 MHz, CDCl3) 7.17–
7.13–7.15 (4H, m, ArH), 6.84–6.94 (8H, m, ArH), 4.38 (2H, t, J 7.5 Hz,
meso CH), 2.05 (4H, m, CH2(CH2)3CH2), 1.29 (6H, m, CH2(CH2)3CH2);
dC (75 MHz, CDCl3) 148.8, 126.4, 123.9, 123.5, 41.9, 38.7, 28.9, 27.5;
m/z 429 (Mþ1).
7.19 (2H, m, ArH), 7.02–7.02 (2H, s, ArH), 6.92–6.93 (2H, m, ArH),
4.53 (1H, s, meso CH), 1.82 (1H, br s, exchanged with D2O, OH), 1.27
(6H, s, C(CH3)2); dC (75 MHz, CDCl3) 143.3, 126.5, 126.3, 124.5, 72.7,
53.8, 28.4; m/z 261 (Mþ23).
4.3.5. 1,1,8,8-Tetra(thiophen-2-yl)octane (3e). White solid; [found:
C, 65.10; H, 6.21; S, 29.29. C24H26S4 requires C, 65.15; H, 5.88; S,
28.95%]; Rf (5% EtOAc/hexane) 0.44; mp: 59–60 ꢀC (DCM/hexane);
4.2.12. 1-(3,4-Dimethoxyphenyl)-2,2-di(thiophen-2-yl)ethanol
(2l). White solid; [found: C, 62.21; H, 5.49; S, 18.12. C18H18O3S2
requires C, 62.42; H, 5.20; S, 18.49%]; Rf (15% EtOAc/hexane) 0.75;
mp: 60–62 ꢀC (DCM/hexane); vmax (KBr) 3050, 2830, 1340, 1030,
vmax (KBr) 2870, 1035, 840, 710 cmꢁ1
; dH (300 MHz, CDCl3) 7.11–
7.15 (4H, m, ArH), 6.83–6.91 (8H, m, ArH), 4.38 (2H, t, J 7.5 Hz, meso
CH), 2.05 (4H, m, CH2(CH2)4CH2), 1.29 (8H, m, CH2(CH2)4CH2); dC
(75 MHz, CDCl3) 148.9, 126.4, 123.9, 123.5, 41.9, 38.8, 29.0, 27.6; m/z
443 (Mþ1).
850, 705 cmꢁ1
; dH (300 MHz, CDCl3) 7.24–7.26 (3H, m, ArH), 6.96–
7.11 (1H, m, ArH), 6.69–6.85 (5H, m, ArH), 5.14 (1H, d, J 4.8 Hz,
CHOH), 4.73 (1H, d, J 6.9 Hz, meso CH), 3.84 (3H, s, OCH3), 3.75 (3H,
s, OCH3), 2.35 (1H, d, J 2.7 Hz, exchanged with D2O, OH); dC
(75 MHz, CDCl3) 148.4, 148.3, 144.1, 142.8, 133.9, 126.4, 126.4, 125.6,
124.9, 124.2, 118.9, 110.4, 109.5, 78.0, 55.7, 55.6, 50.8; m/z 369
(Mþ23).
Acknowledgements
A financial assistance (project SR/S1/OC-27/2009) from De-
partment of Science and Technology (DST), Government of India,
New Delhi is gratefully acknowledged. A.S. thanks CSIR for a Senior
Research Fellowship.
4.3. General procedure for synthesis of compounds 3a–e
To
a clear solution of freshly distilled DMSO (0.24 mL,
3.07 mmol) in THF at 0 ꢀC was added a solution of n-BuLi (1.45 mL,
3.33 mmol) and the reaction mixture was stirred for 15 min. To this
bis(thien-2yl)methane 1 (500 mg, 2.17 mmol) dissolved in THF was
added through cannula at same temperature. The reaction mixture
was stirred for 30 min, whereupon a turbid red coloured anion was
generated. The electrophile (1.08 mmol) dissolved in dry THF
(10 mL) was then added dropwise, and the reaction mixture was
stirred for 30 min, quenched with saturated aqueous solution of
NH4Cl. The reaction mixture was extracted with ethyl acetate
(20 mLꢂ3), the combined organic phases were dried over Na2SO4,
filtered and solvent was removed under reduced pressure. The
product was purified by flash chromatography using silica gel (60–
120 mesh) and mixture of ethyl acetate/hexanes as eluents. The
yields of the purified products 3a–e are reported in Table 2.
References and notes
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Bentabed-Ababsa, G.; Chevallier, F.; Yonehara, M.; Uchiyama, M.; Derdour, A.;
Mongin, F. Chem. Commun. 2008, 5375; (e) Snieckus, V. Chem. Rev. 1990, 90, 879;
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4.3.1. 1,1,4,4-Tetra(thiophen-2-yl)butane (3a). White solid; [found:
C, 61.88; H, 4.67; S, 33.07. C20H18S4 requires C, 62.17; H, 4.66; S,
33.16%]; Rf (5% EtOAc/hexane) 0.41; mp: 114–115 ꢀC (DCM/hexane);
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vmax (KBr) 2870, 1080, 1035, 845, 700 cmꢁ1
; dH (300 MHz, CDCl3)
7.13–7.15 (4H, m, ArH), 6.84–6.91 (4H, m, ArH), 6.77–6.84 (4H, m,
ArH), 4.44 (2H, br s, meso CH), 2.13 (4H, m, CH2CH2); dC (75 MHz,
CDCl3) 144.0, 126.9, 125.3, 125.0, 38.5, 37.8; m/z 387 (Mþ1).
4.3.2. 1,1,5,5-Tetra(thiophen-2-yl)pentane (3b). White solid; [found:
C, 62.86; H, 5.37; S, 32.17. C21H20S4 requires C, 63.00; H, 5.00; S,
32.00%]; Rf (5% EtOAc/hexane) 0.41; mp: 105–106 ꢀC (DCM/hex-
ane); vmax (KBr) 2860, 1080, 1035, 850, 700 cmꢁ1
; dH (400 MHz,
CDCl3) 7.07–7.12 (4H, m, ArH), 6.87–6.92 (4H, m, ArH), 6.77–6.82
(4H, m, ArH), 4.36 (2H, t, J 7.6 Hz, meso CH), 2.11 (4H, m,
CH2CH2CH2), 1.37 (2H, m, CH2CH2CH2); dC (100 MHz, CDCl3) 148.5,
126.4, 124.0, 123.6, 41.6, 38.4, 25.7; m/z 401 (Mþ1).
4.3.3. 1,1,6,6-Tetra(thiophen-2-yl)hexane (3c). White solid; [found:
C, 63.95; H, 5.49; S, 30.72. C22H22S4 requires C, 63.76; H, 5.31; S,
30.91%]; Rf (5% EtOAc/hexane) 0.44; mp: 90–92 ꢀC (DCM/hexane);
13. (a) Kurata, H.; Kim, S.; Fujimoto, T.; Matsumoto, K.; Kawase, T.; Kubo, T. Org. Lett.
2008, 10, 3837; (b) de Jong, J. J. D.; Browne, W. R.; Walko, M.; Lucas, L. N.;
vmax (KBr) 2860, 1080, 1036, 845, 710 cmꢁ1
; dH (300 MHz, CDCl3)