Helvetica Chimica Acta Vol. 87 (2004)
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9H-Fluoren-4-ol (1d): Yellow solid (391 mg, 84%). M.p. 107 1088. FT-IR: 3303, 1583, 1479, 1448, 1259.
1H-NMR: 3.94 (s, CH2); 5.22 (s, OH); 6.75 (m, 1 H); 7.17 (m, HÀC(3) and HÀC(2)); 7.30 (ddd, J 7.5, 7.5, 1.5,
HÀC(6) or HÀC(7)); 7.40 (t, J 7.8, HÀC(6) or HÀC(7)); 7.54 (d, J 7.5, 1 H); 8.13 (d, J 7.5, 1 H). MS: 182
(100, M ), 181 (45), 165 (15), 152 (40).
Spiro[fluorenopyran-thioxanthenes] 3a d: General Procedure. A suspension of 9H-thioxanthen-9-one
(2.00 g, 9.43 mmol), and lithium acetylide ethane-1,2-diamine complex (3.00 g, 29.4 mmol) in dry THF (250 ml)
was stirred under Ar for 24 h. The suspension was treated with H2O (200 ml), the aq. phase extracted with Et2O
(3 Â 100 ml), and the combined org. phase dried (Na2SO4) and evaporated. The obtained crude product was
divided into four fractions, and each one was submitted to flash column chromatography (10% AcOEt/hexane;
not more than 30 min): almost pure 9-ethynyl-9H-thioxanthen-9-ol (2; 1.5 g, 67%).
A soln. of 2 (1.30 mg, 5.50 mmol), 9H-fluorenol 1a d (0.200 g, 1.10 mmol), pyridinium p-toluenesulfonate
(50 mg) and CHCl3 (60 ml) was refluxed for 2.5 h under an Ar. Solvent evaporation gave a brown oil, which was
purified by CC (0 3% AcOEt/hexane). Recrystallization from Et2O/pentane gave a crystalline material.
Spiro[fluoreno[1,2-b]pyran-2(11H),9'-[9H]thioxanthene] (3a): Pale yellow solid (160 mg, 36%). M.p.
249 2508. FT-IR: 3054, 1612, 1454, 1230, 1203. 1H-NMR: 4.04 (s, CH2); 6.13 (d, J 9.9, HÀC(3)); 6.41(d, J
9.9, HÀC(4)); 7.07 (d, J 7.5, 1 H); 7.28 (m, 4 H); 7.40 (m, 3 H); 7.49 (m, 2 H); 7.60 (d, J 7.5, 1 H); 7.80 (m,
3 H). 13C-NMR: 33.8 (CH2); 79.8 (C(2)); 113.0; 117.7; 120.1; 121.1; 121.9; 125.3; 125.8; 126.2; 126.7; 126.8;
126.98; 127.01; 127.6; 128.1; 129.1; 138.8; 141.5; 143.6; 144.5; 149.4. MS: 402 (100, M ), 221 (70), 196 (12), 152
(25). HR-MS: 402.1075 (C28H18OS ); calc. 402.1078).
Spiro[fluoreno[2,3-b]pyran-2(10H),9'-[9H]thioxanthene] (3b): Yellow solid (102 mg, 23%). M.p. 229
2308. FT-IR: 3056, 2923, 1662, 1454, 1214. 1H-NMR: 3.94 (s, CH2); 6.12 (d, J 10.2, HÀC(3)); 6.44 (d, J 10.2,
HÀC(4)); 7.30 7.20 (m, 6 H); 7.36 (dd, J 7.5, 7.5, HÀC(7) or HÀC(8)); 7.40 (s, HÀC(5) or HÀC(11)); 7.48
(m, 2 H); 7.53 (d, J 7.5, 1 H); 7.68 (d, J 7.5, 1 H); 7.84 (m, 2 H). 13C-NMR: 36.3 (CH2); 79.8 (C(2)); 106.7;
118.2; 120.1; 121.5; 122.3; 123.1; 125.1; 126.1; 126.7; 126.9; 127.0 (2 C); 127.6; 129.1; 136.0; 128.7; 141.5; 143.6;
144.3; 152.8. MS: 402 (100, M ), 221 (55), 201 (15), 152 (15). HR-MS: 402.1064 (C28H18OS ; calc. 402.1078).
Spiro[fluoreno[3,2-b]pyran-2(6H),9'-[9H]thioxanthene] (3c): Yellow solid (71 mg, 16%). M.p. 201 2028.
FT-IR: 3054, 1610, 1454, 1428, 1230. 1H-NMR: 3.86 (s, CH2); 6.12 (d, J 9.9, HÀC(3)); 6.38 (d, J 9.9,
HÀC(4)); 7.16 (s, HÀC(5) or HÀC(11)); 7.30 7.24 (m, 6 H); 7.32 (ddd, J 7.5, 7.5, 1.2, HÀC(8) or HÀC(9));
7.42 (dd, J 7.5, 1 H); 7.53 7.46 (m, 4 H); 7.55 (d, J 7.5, 1 H); 7.79 (d, J 7.5, 1 H); 7.89 (m, 2 H). 13C-NMR:
36.2 (CH2); 79.7 (C(2)); 106.6; 118,1; 120.0; 121.4; 122.1; 123.0; 125.0; 126.0; 126.6; 126.8; 126.9; 127.5; 129.0;
135.9; 138.6; 141.4; 143.5; 144.2; 152.7; 170.7. MS: 402 (100, M ), 221 (55), 196 (15), 152 (12). HR-MS: 402.1079
(C28H18OS ; calc. 402.1078).
Spiro[fluoreno[4,3-b]pyran-2(7H),9'-[9H]thioxanthene] (3d): Light orange solid (160 mg, 36%). M.p.
243 2448. FT-IR: 3054, 1614, 1455, 1428, 1232, 1205. 1H-NMR: 4.07 (s, CH2). 6.26 (d, J 9.9, HÀC(3)); 6.48 (d,
J 9.9, HÀC(4)); 7.02 (d, J 7.5, HÀC(5) or HÀC(6)); 7.19 (d, J 7.5, HÀC(5) or HÀC(6)); 7.34 (m, 4 H); 7.39
(m, 2 H); 7.61 (m, 3 H); 8.00 (m, 2 H); 8.39 (m, 1 H). 13C-NMR: 37.4 (CH2); 80.0 (C(2)); 117.6; 117.6; 121.2;
121.3; 123.9; 124.5; 125.4; 125.6; 126.2; 126.7; 127.0; 127.1; 127.5; 127.9; 129.1; 138.9; 140.2; 142.8; 146.0; 148.7;
170.6. MS: 402 (25, M ), 221 (10), 192 (30), 149 (40), 105 (100). HR-MS: 402.1071 (C28H18OS ; calc. 402.1078).
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