The title compound (I), having distinct laxative properties, was prepared (all m.ps. are corrected).1,3-C6H4(OH)2 (22.0 g.), 45.2 g. ο-BzC6H4OH, and 5.0 g. anhydrous ZnCl2 stirred 2.5 hrs. at 120°, 150 ml. EtOH added to the hot sticky mass, the mixture refluxed until solution occurred, the solution poured into 1200 ml. slightly acidic H2O, and the precipitated mass treated with boiling H2O and cooled gave 53.5-62.3 g. crude 3-phenyl-3-(2,4-dihydroxyphenyl)phthalide (II), gray powder, m. 130-48°.Crude II refluxed with 1600 ml. absolute Et2O, the insoluble precipitate (9.8-15.4 g., m. 276-85°) filtered off, the filtrate evaporated to 200 ml. (the filtrate partially evaporated yielded addnl. product), and the product dried at 120° gave 30.5-9.0 g. (total yield) II, m. 195-9° (pure II m. 199.0-200.0°).II subjected to the oxime splitting of Friedlander (cf. Hubacher, C.A. 40, 34257), gave a small amount 4-phenyl-1H-2,3-benzoxazin-1-one (III), m. 163.0-3.5° (EtOH), mixed m.p. with III (m. 162.5-3.0) [Thorp, Ber. 26, 1262, 1795(1893)] 162.7-3.1° [di-Ac derivative m. 141.0-1.9° (EtOH)].II (3.18 g.), 3.8 ml. MeI, 2.8 g. K2CO3, and 50 ml. Me2CO heated 6 hrs. at 60° and recrystallized from EtOH (1 g./16 ml.) gave II di-Me ether, m. 157.0-8.5°.Raney alloy (5 g.) added during 20 min. to 15.9 g. II in 60 ml. 2.5N NaOH with stirring (temperature rose to 55-60°), when the orange color disappeared the mixture filtered, the filtrate acidified, the gummy precipitate treated with hot H2O, and cooled overnight gave 14.7-15.5 g. crude ο-(2,4-dihydroxybenzhydryl)benzoic acid (IV), m. 175-81°.Crude IV dissolved in absolute Et2O (1 g./30 ml.), the solution filtered, the filtrate evaporated to 5 ml., and the product dried at 120° gave in 2 crops, 7.6-10.4 g. IV, m. 184-6°; pure IV m. 186.9-7.4°.IV (8.0 g.) in 200 ml. Et2O treated with CH2N2 (from 5.2 g. nitrosomethylurea), most of the Et2O evaporated, and the resulting crystals dissolved in a large volume of Et2O, and most of the Et2O distilled or crystallized from 1:5 MeOH-C6H6 gave the Me ester, m. 203.6-4.4°.IV (3.2 g.) in 5 ml. Ac2O and 0.03 ml. concentrated H2SO4 heated 30 min. to 120°, the crude material recrystallized from 230 ml. EtOH, and then recrystallized from EtOAc (1 g./12 ml.) gave 10-(2,4-dihydroxyphenyl)-9-anthrol tri-Ac derivative, m. 183.4-4.0°, mixed m.p. not depressed.IV (1.60 g.) heated to 220° and the resulting compound crystallized from EtOH (1 g./12 ml.) or sublimed in vacuo gave α-(2,4-dihydroxyphenyl)-α-phenyl-ο-toluic acid ε-lactone (V), m. 242.0-2.5°.V (0.75 g.) in 10 ml. N Na2CO3 refluxed 5 hrs. under N and the resulting solution acidified gave IV.V (1.0 g.), 1.5 ml. Ac2O, and 0.02 ml. concentrated H2SO4 heated 30 min. to 120° and the product recrystallized from 12 ml. EtOAc gave 0.78 g. Ac derivative (VI), m. 174.6-5.3°; VI was also obtained by acetylating IV with Ac2O and NaOAc.V (3.02 g.), MeI, 1.4 g. K2CO3, and 50 ml. Me2CO heated 8 hrs. at 60° and the product recrystallized from EtOH (1 g./80 ml.) gave α-(2-hydroxy-4-methoxyphenyl)-α-phenol-ο-toluic acid ε-lactone, m. 191.9-2.7°.IV (12.8 g.) reduced with 5.0 g. LiAlH4 in 500 ml. Et2O in a Soxhlet apparatus (24 hrs. reflux), worked up, the Et2O layer evaporated, the residue dissolved in 200 ml. 20% EtOH, the solution slowly cooled with stirring, and the product (10.4-11.2 g.) recrystallized from H2O (1 g./450 ml.) gave I, m. 169.8-70.4°.I (3.06 g.), 6 ml. Ac2O, and 0.02 ml. concentrated H2SO4 heated 1 hr. to 100°, the dry crude product (4.1-4.4 g.) placed in a thimble, extracted with Et2O, and the extract let stand several days at 5° gave 3.1-3.6 g. tri-Ac derivative, m. 104.1-5.5°.I (1.0 g.) in 2 ml. C5H5N treated with 2 ml. BzCl, the mixture kept 0.5 hr. at 120°, poured into ice H2O, the gummy precipitate washed free from C5H5N, and recrystallized from a large volume of EtOH gave the tri-Bz derivative, m. 141.1-2.2°.
