Beilstein J. Org. Chem. 2016, 12, 716–724.
1b–f, the presence of thiirane and the corresponding ethylene 13C NMR (150 MHz, CDCl3) δ 151.2, 149.8, 144.0, 142.9 (for
was evidenced based on the 1H NMR spectra. In these cases, no 8 Carom), 131.3, 131.1, 130.5, 127.5, 127.1, 127.0, 126.6, 126.1,
isolation of the thiirane was performed; after addition of 125.4, 125.2, 125.0 (for 32 CHarom), 78.8, 78.4 (C-4 + C-5, for
tris(dimethylamino)phosphine desulfurization leading to the cis and trans), 55.4, 55.3 (C-2, cis and trans) 33.1 (CH3-cis),
ethane derivative was carried out.
32.9 (for 2 CH3-trans), 32.5 (CH3-cis) ppm; anal. calcd for
C25H22S4 (450.70): C, 66.62; H, 4.92; S, 28.46; found: C,
Reaction of thioketones 1d–e with (trimethylsilyl)diazo- 66.46; H, 4.91; S, 28.33.
methane (7c) – General procedure: The corresponding
thioketones 1d–e (1 mmol) were dissolved in freshly distilled 1,1-Di(thiophen-2-yl)-propene (9k): Yield: 52 mg (25%) –
THF (2.5 mL) and the solution was cooled to −75 °C (acetone/ After desulfurization of tiirane 8k. Yellow oil; IR (film) ν: 3104
dry ice). Then, the mixture was treated with small portions of an (w), 3071 (w), 2930 (w), 2908 (w), 2850 (w), 1438 (m), 1362
ethereal solution of 7c (1 mmol). The mixture was kept in a (w), 1249 (m), 1223 (m), 1036 (w), 850 (s), 836 (s), 818 (s),
cold bath, and the intense color of the thioketone vanished after 695 (s) cm−1; 1H NMR (600 MHz, CDCl3) δ 7.23–7.22 (m, 1H,
15 min. Subsequently, the mixture was allowed to slowly warm Harom), 7.01–7.00 (m, 1H, Harom), 6.96–6.94 (m, 1H, Harom),
to rt (ca. 2–4 h). After removal of the solvent under vacuum, the 6.90–6.89 (m, 1H, Harom), 6.80–6.79 (m, 1H, Harom), 6.71–6.70
residue was subjected to the 1H NMR analysis in CDCl3 solu- (m, 1H, Harom), 6.18 (q, J = 7.2 Hz, 1H, =CH), 1.74 (d, J = 7.2
tion with a weighed amount of 1,1,2,2-tetrachloroethane Hz, 3H, CH3) ppm; 13C NMR (150 MHz, CDCl3) δ 129.4,
as an internal standard. Crude products were purified by CC 139.8, 146.8 (2 Carom, Carom, C=), 127.6, 127.0, 126.6, 126.3,
(CHCl3/hexane 2:8).
125.5, 124.8, 123.4 (6 CHarom, =CH), 15.6 (CH3) ppm; anal.
calcd for C11H10S2 (206.33): C, 64.04; H, 4.89; S, 31.08;
2,2-Dimethyl-3,3-diphenylthiirane (8a): Yield: 182 mg found: C, 63.83; H, 4.98; S, 31.14.
(76%). White crystals; mp 66–67 °C (chromatographic purifica-
tion); IR (KBr) ν: 2987 (w), 2921 (w), 1596 (w), 1490 (m), 2-Trimethylsilyl-4,4,5,5-tetra(thiophen-2-yl)-1,3-dithiolane
1443 (m), 773 (m), 747 (m), 705 (s), 691 (m) cm−1; 1H NMR (10r): Yield: 220 mg (87%). Yellow crystals: mp 152–154 °C
(600 MHz, CDCl3) δ 7.60–7.58 (m, 4H, Harom), 7.31–7.29 (m, (hexane/CH2Cl2); IR (KBr) ν: 2951 (w), 1618 (w), 1424 (m),
4H, Harom), 7.23–7.21 (m, 2H, Harom), 1.62 (s, 6H, CH3) ppm; 1250 (s), 1232 (m), 1122 (m), 1077 (m), 1050 (m), 842 (s),
13C NMR (150 MHz, CDCl3) δ 142.4 (for 2 Carom), 129.4, 752 (s), 699 (s), 632 (m) cm−1; 1H NMR (600 MHz, CDCl3) δ
127.9, 126.8 (for 10 CHarom), 67.8, 52.9 (C-2, C-3), 27.9 7.23–7.22 (m, 2H, Harom), 7.20–7.19 (m, 2H, Harom), 6.96–6.95
(2 CH3) ppm; ESIMS m/z (%): 241 (100, [M + H]+); anal. calcd (m, 2H, Harom), 6.89–6.87 (m, 2H, Harom), 6.83–6.81 (m, 4H,
for C16H16S (240.36): C, 79.95; H, 6.71; S, 13.34; found: C, Harom), 3.89 (s, 1H, ((CH3)3Si)HC), 0.34 (s, 9H, (CH3)3Si)
79.69; H, 6.50; S, 13.40.
ppm; 13C NMR (150 MHz, CDCl3) δ 148.1, 146.1 (for 4
Carom), 130.2, 129.4, 127.0, 125.6, 125.5, 125.4 (for 12
1,1-Di(thiophen-2-yl)-2-methylpropene (9d): Yield: 4 mg CHarom), 74.9 (C-4, C-5), 36.5 (C-2), −1.53 ((CH3)3Si) ppm;
(2%). Yellow oil; IR (film) ν: 2927 (w), 2908 (w), 2850 (w), anal. cald for C22H22S6Si (506.89): C, 52.13; H, 4.37; S, 37.96;
1436 (m), 1369 (m), 1227 (m), 1016 (w), 827 (m), 693 (s) found: C, 52.44; H, 4.55; S,37.71.
cm−1; 1H NMR (600 MHz, CDCl3) δ 7.29 (d, J = 5.4 Hz, 2H,
Harom), 7.04–7.02 (m, 2H, Harom), 6.91 (d, J = 3.6 Hz, 2H,
Supporting Information
Harom), 2.03 (s, 6H, CH3) ppm; 13C NMR (150 MHz, CDCl3)
δ 144.9, 137.1 (Carom, Carom-C=), 126.6, 126.4, 124.9 (for 6
Supporting Information File 1
CHarom), 122.9 (C=C(CH3)2), 23.3 (2 CH3) ppm; anal. calcd for
C12H12S2 (220.35): C, 65.41; H, 5.49; S, 29.10; found: C,
65.31; H, 5.76; S, 28.81.
Experimental data for selected compounds 8–10, and the
original 1H and 13C NMR spectra for all products.
2,2-Dimethyl-4,5-diphenyl-4,5-di(thiophen-2-yl)-1,3-dithio-
lane (10f): Isolated as a mixture of cis-, trans-isomers
(crude product ratio 65:35). Yield: 142 mg (63%).
White crystals; mp 153–154 °C (MeOH/CHCl3);
IR (KBr) ν: 3062 (w), 2919 (w), 1595 (w), 1490 (m), 1443 (m),
1231 (m), 1156 (m), 854 (w), 697 (s) cm−1; 1H NMR
(600 MHz, CDCl3) δ 7.59–6.68 (m, 32H, Harom), 1.86 (s, 3H,
CH3-cis), 1.70 (s, 6H, CH3-trans), 1.39 (s, 3H, CH3-cis) ppm;
Acknowledgements
The authors thank the National Science Center (Cracow,
Poland) for generous financial support (Grant Maestro-3 (Dec-
2012/06/A/ST5/00219). Skilful performance of microanalyses
by Ms Hanna Jatczak and Ms Agnieszka Cieślińska (University
of Łódź) is gratefully acknowledged.
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