Reaction Steps
To a solution of 1-chloro-5-hydroxymethyl-dibenzo [a,d]cycloheptene (8.3 g) in dichloromethane (80 ml) was added p-toluenesulphonyl chloride (6.3 g), pyridine (5.11 g), and 4-dimethylamino pyridine (150 mg). The reaction mixture was refluxed for 15h, cooled washed with water (2×80 ml), dried (Na2SO4), filtered and concentrated in vacuo to leave an oil which was purified by chromatography on flash silica with 15% ethyl acetate in hexane as eluent. The purified tosylate was dissolved in glacial acetic acid (100 ml) with anhydrous sodium acetate (4.4 g) and the solution refluxed for 15h. The mixture was concentrated in vacuo to leave a residue which was partitioned between dichloromethane (3×100 ml) and water (100 ml). The combined organic layers were dried (Na2SO4), filtered and concentrated in vacuo to leave a residue which was dissolved in 75% aqueous methanol (160 ml) and treated at 0° C. with potassium hydroxide (10 g). After 14h the reaction mixture was concentrated in vacuo. Chromatography of the residue on flash silica with 15% ethyl acetate in hexane as eluent gave the less polar isomer, 1-chloro-5-hydroxydibenzo[a,e]cyclooctene (1.5 g), m.p. 158°-160° C. δ(360 MHz, CDCl3) 3.12 (1H, dd, J =1.51 and 10.2 Hz, CHAHB --CHOH), 3.63 (1H, dd, J=15.1 and 6.9 Hz, CHAHB --CHOH), 5.57 (1H, dd, J=10.2 and 6.9 Hz, CHAHB --CHOH), 6.74 (1H, d, J=11.9 Hz, ArCHD =CHE --Ar), 7.03 (1H, d, J=11.9 Hz, ArCHD =CHEAr) and 7.07-7.46 (7H, m, aromatics). m/e 256 (M+). i.r.(νmax, nujol) 3350-3100 cm-1 (br, OH). Found: C, 74.5; H, 5.1. C16H13C10 requires: C, 74.9; H, 5.1%. Further elution gave the more polar isomer, 1-chloro-6-hydroxy-dibenzo[a,e]cyclooctene (0.47 g), m.p. 144°-146° C. δ(360 MHz, CDCl3) 3.39 (2H, m, CH--CHOH), 5.13 (1H, m, CH2 --CHOH), 6.77 (1H, d, J=11.9 Hz, Ar--CHA =CHB), 7.02 (1H, d, J=11.9 Hz, ArCHA =CHB) and 7.07-7.38 (7H, m, aromatics). m/e 256 (M+). i.r (νmax, nujol) 3300-3100 cm-1 (br, OH). Found: C, 74.8; H, 5.2. C16H13C10 requires: C, 74.9; H, 5.1%.
