Ungnade, Herbert E. published the artcileCondensations of aromatic aldehydes and aryl carbinols with aluminum chloride and aromatic systems, Quality Control of 596-38-3, the publication is Journal of the American Chemical Society (1953), 3333-6, database is CAplus.
The reaction of aryl carbinols and aromatic aldehydes with aromatic hydrocarbons and excess AlCl3 has been extended to include substituted benzyl alcs. as donors and mesitylene, Ph2, and Ph2O as acceptor mols. An unexpected reaction occurred in Ph2O with formation of 9-phenylxanthydrol (I) from BzH, PhCH2OH, or Ph2CHOH. The formation of I in these reactions is unique since the oxygenated compounds apparently undergo condensation at the normally unreactive o-positions of the Ph2O rather than cleavage. BzH (30 g.) added during 0.5 h. with stirring to 20 g. Ph2 and 79 g. AlCl3 at 60°, the mixture stirred 3.5 h. at 60°, decomposed, and steam-distilled, the nonvolatile fraction (32.39 g.) distilled in vacuo, and the distillate (6.02 g., 28%), b0.001 170-210°, crystallized 3 times from ligroine gave diphenylanthracene (II), m. 202-3°, λmaximum 230 mμ (log ε 4.65), 257.5 (4.97), 277.5 (5.09), 332.5 (3.67), 347.5 (3.91), 365 (4.01), 385 (3.89). II (1 g.) in 14 cc. glacial AcOH refluxed gently over a low flame and treated slowly during 0.5 h. with 4.0 g. CrO3 in 4 cc. H2O and 16 cc. AcOH, the solution cooled, diluted with 200 cc. H2O, and filtered, and the crude green solid washed with H2O, dilute aqueous NaOH, and again H2O, and recrystallized from 95% EtOH and dried in vacuo at 100° gave 1.02 g. (93.5%) diphenylanthraquinone, yellow needles, m. 270-1°. BzH (25 g.) added during 0.5 h. to 67 g. AlCl3 in 60 cc. mesitylene, the mixture stirred 3.5 h. at 60°, decomposed and steam-distilled, the distillate taken up in C6H6, washed with saturated aqueous NaHSO3 [the insoluble adduct gave 7.86 g. (31%) BzH (oxime, m. 32-3°)], and the C6H6 solution rectified yielded 1.0 g. (2%) xylenes, b598 140-50°, nD23 1.4970, λmaximumEtOH 266 mμ (log ε 2.40), 8.7 g. (17%) trimethylbenzenes, b600 150-60°, nD23 1.5005, λmaximumEtOH 266 mμ (log ε 2.40) [gave nitrated 2,4,6-(O2N)3C6Me3, m. 230-2°], and 2.6 g. (4%) C6H2Me4, b600 180-5°, nD23 1.5105, λmaximum 269 mμ (log ε 2.57); a portion (12.86 g.) of the nonvolatile residue (22.50 g.) refluxed with ligroine (b. 70-90°), the solution filtered from 2.74 g. insoluble material, the solution adsorbed on Al2O3, and the resulting 3 bands (blue fluorescing under UV light) eluted with ligroine gave 7.34 g. (45.7%) oily solid, m. 132-8°, which gave, after repeated recrystallization from ligroine, tetramethylanthracene, m. 148-8.7°, λmaximum 338 mμ (log ε 3.45), 350 (3.66), 366 (3.78), 386 (3.68). BzH (25 g.), 67 g. AlCl3, and 75 cc. Ph2O treated in the usual manner, the steam distillate extracted with Et2O, the extract washed with H2O, dried, and distilled gave 1.2% unreacted BzH (b19 96-8°) and 44.3% recovered Ph2O [identified as (p-H2NSO2C6H4)2, m. 157-8°]; the semi-solid residue from the steam distillation taken into C6H6, washed, dried, and distilled gave 32.2 g. distillate; a 2.18-g. portion in C6H6 gave 4 distinct bands on Al2O3; the bulk of the product was contained in 3 bands which were eluted with C6H6 and gave 0.12 g. red viscous oil, 1.48 g. red-brown oil, and 0.46 g. I crystalline solid, m. 149-54° (from ligroine); distillation of the residue (9.55 g.) gave 4.15 g. red oil, b0.001 190-210°, which solidified on standing to yield 3.02 g. I, m. 156-7° (from C6H6-ligroine); on distillation in vacuo of larger quantities of the residue, pyrolysis and reduction occurred to yield PhOH and 9-phenylxanthene. Similar results were obtained with PhCH2OH and Ph2CHOH as starting materials, the over-all yields of I being from BzH 15.5%, from PhCH2OH 15%, and from Ph2CHOH 27%. I, m. 157-8°, was also obtained in 76% yield from xanthone and PhMgBr. I dissolved with green-yellow color and fluorescence in concentrated H2SO4; it gave derivatives with semicarbazide (m. 206-7°), NH2OH (m. 194-5°), and PhNHNH2 (m. 127-8°); it was recovered unchanged from its reaction mixture with MeMgI, and with acylating and oxidizing agents under ordinary conditions; pyrolyzed at 282° it gave PhOH. I was reduced to 9-phenylxanthene (III), m. 142-3° (from ligroine), by a Clemmensen reduction (91.3%), by a Schmidt reaction (96.6%), and by refluxing with alc. HCl (87.7%); insoluble in concentrated H2SO4, gave oxidized with KMnO4 in aqueous Me2CO, I, m. 155-6° (from ligroine). Xanthone (IV) (5 g.) in dry C6H6 added to 0.025 mol PhCH2MgCl in dry Et2O, the complex decomposed with ice and aqueous NH4Cl, and the resulting yellow oil triturated with petr. ether, recrystallized from ligroine, or chromatographed on Al2O3 yielded 89% crystalline benzalxanthene (V), yellow needles, m. 110-11°, yellow with green fluorescence in cold concentrated H2SO4. The reduction of 2.65 g. V with HI and Ac2O cleaved at the 9,10 double bond to give 0.11 g. IV, m. 158-60° (recrystallized m. 173-4°), and 0.74 g. 9-benzylxanthene (VI), m. 69-70°. p-PhOC6H4Bz (VII), m. 69.2-9.4°, was prepared by the method of Kipper [Ber. 38, 2490(1905)]; soluble with yellow color in cold concentrated H2SO4; unchanged under the conditions of the cyclodehydration procedure of Bradsher (C.A. 34, 6265.4); cleaved by fusion with NaOH at 350° to give BzOH, Ph2O, and traces of PhOH and p-HOC6H4Bz; and showed strong IR absorption at 6.05 and 8.02, and 10 addnl. bands common to PhBz and Ph2O. VII (2.0 g.) in 100 cc. 95% EtOH hydrogenated at 30 mm. pressure with 3 g. Raney Ni and 1 drop 50% aqueous KOH as catalyst, the mixture filtered, the solvent removed, and the residue crystallized from petr. ether gave 1.70 g. (85%) p-PhOC6H4CH(OH)Ph (VIII), m. 75.8-6.9°. VII (20 g.) added to amalgamated Zn (from 100 g. Zn and 10 g. HgCl2) and 100 cc. concentrated HCl, the mixture refluxed 12 h. while 3 fresh 50-cc. portions concentrated HCl were added, the product extracted with C6H6, the extract washed neutral, dried, and evaporated, the residue (19.67 g.) sublimed from a mol. still at 0.001 mm., and the colorless distillate (9.34 g.) resublimed to give 8.61 g. colorless liquid which solidified on standing to give p-PhOC6H4CH2Ph (IX), m. 41-2°; the 2nd fraction from the mol. distillation, a viscous oil, which set to a glassy solid in the side arm, is believed to be the corresponding pinacol p-MeOC6H4CH2OH (33 g.) added during 1 h. to 75 g. AlCl3 in 160 cc. C6H6, and the mixture worked up as usual gave unreacted C6H6, b606 72-5°, nD25 1.4952, 11.8 g. PhOMe, b19 75-8°, nD23 1.5147 [redistilled 8.4 g. (43%), b606 144°, nD22 1.5157, identified as 2,4-(O2N)2C6H3OMe, m. 84-5°], and 3.2 g. anthracene (X), b19 155-60°, colorless plates, m. 212-13°; an addnl. amount X, m. 210-11°, was obtained by decolorizing the still residue with Nuchar and recrystallizing To establish the composition of the binary mixture X-H2O, 1.0 g. pure X was steam-distilled at 97°/603 mm. to furnish 0.49 g. X in 5 l. distillate during 1 h.; the binary mixture contained thus 0.0098% X. X (1 g.) and 10 g. PhOMe steam-distilled at 98°/605 mm. yielded 5 l. distillate in 1 h. containing 0.30 g. X. 3,4-(MeO)2C6H3CH2OH (0.148 mol) gave with 0.297 mol AlCl3, and 150 cc. thiophene-free C6H6, by the general procedure, 1.34 g. guaiacol (phenylurethane, m. 134°) and 1.03 g. X, m. 211-12°. To 0.20 mol o-HOC6H4CH2OH and 150 cc. C6H6 was added 0.40 mol AlCl3 in small portions, and the mixture worked up as usual to give 0.61 g. PhOH and 2.47 g. X. To 10 g. LiAlH4 in 180 cc. dry Et2O was added with stirring 34.50 g. o-PhCH2C6H4CO2H, m. 110-11°, in 100 cc. Et2O at such a rate as to keep the mixture refluxing gently, the mixture stirred 0.5 h. and decomposed cautiously with cooling with 100 cc. H2O, and then with 10% aqueous H2SO4, and the Et2O layer washed with 10% aqueous Na2CO3, dried, and evaporated to give 20.47 g. (64.5%) o-PhCH2C6H4CH2OH (XI), b0.001 130-2°. XI (10 g.) in 50 cc. C6H6 gave with 20 g. AlCl3, by the general procedure, 5.00 g. X, m. 212-14° (sublimed at 160-200°/1-2 mm.). XI (10 g.) treated in exactly analogous manner with 75 cc. PhMe and 0.15 mol AlCl3 yielded 11.08 g. non-volatile residue which gave 4.76 g. dimethylanthracene, m. 215-17° (from ligroine); the volatile fraction contained 4.02 g. (47.8%) Ph2CH2, b. 260-2° (identified as BzPh, m. 47-8°). The UV absorption maximum in mμ and in parentheses the log ε values in 95% EtOH are listed for: Ph2O 225 shoulder (4.01), 271 (3.31); p-PhOC6H4Me, 225 (4.06), 278 (3.30); 3,4-Me2C6H3OPh, 226 shoulder (4.05), 278 (3.32); VIII, 233 (4.18), 265 (3.27); IX 228 shoulder (4.21), 271 (3.47); VII, 286 (4.24); xanthene, 247 (3.88), 283 (3.36); III, 250 (3.91) 284 (3.47); VI, 243 (3.94), 283 (3.50), 338 (2.37); V, 252 shoulder (4.10), 284 (3.89), 341 (4.08); xanthydrol, 239 (4.17), 290 (3.59), 336 (2.69); I, 244 (4.10), 290 (3.61); 1-(9-phenylxanthyl)-semicarbazide, 245 (4.11), 290 (3.69); IV, 260 (4.11), 288 (3.66), 336 (3.85). The UV absorption spectra of I and III are recorded in Document 3953 ADI Auxiliary Publications Project, Photoduplication Service, Library of Congress, Washington, D.C.
Journal of the American Chemical Society published new progress about 596-38-3. 596-38-3 belongs to alcohols-buliding-blocks, auxiliary class Other Aromatic Heterocyclic,Benzene,Alcohol, name is 9-Phenyl-9H-xanthen-9-ol, and the molecular formula is C14H20BClO2, Quality Control of 596-38-3.
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https://en.wikipedia.org/wiki/Alcohol,
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