Dauben, Wm. G. published the artcileThe hydrogenation of 4-hydroxybiphenylcarboxylic acids, Product Details of C13H16O2, the publication is Journal of the American Chemical Society (1953), 4969-73, database is CAplus.
When p-(p-HOC6H4)H6H4CO2H (I) was hexahydrogenated over Raney Ni in alkali, reaction occurred only in the HO-substituted ring and both a cis and a trans isomer were isolated. The perhydrogenation yielded only 1 pure product which was shown to have the trans configuration in the CO2H-substituted ring. When m-(p-HOC6C4)C6H4CO2H (II) was hexahydrogenated, again reaction occurred only in the HO-substituted ring but only 1 isomer was isolated. p-(p-MeOC6H4C6H4)CO2H (40 g.) heated 15 hrs. under N with 525 cc. AcOH and 105 cc. 48% HBr, 300 cc. solvent distilled off in vacuo, the residual solution diluted with 300 cc. H2O, cooled, and the crude product (35 g.) recrystallized from dioxane, cyclohexane, and then dilute AcOH gave 30 g. (80%) I, m. 288-90° (uncorrected). I (4.0 g.), 1.0 g. Na2CO3, and 2 cc. Raney Ni W-2 suspended in 31 cc. H2O, the mixture hydrogenated 6 hrs. at 125° and 2500 lb. pressure and then 0.75 hr. at 150°, filtered, the filtrate (150 cc.) acidified with excess concentrated HCl, the precipitate (2.9 g.), m. 220-32°, refluxed 8 hrs. with 100 cc. MeOH and 2 cc. concentrated H2SO4, the solution concentrated to 25 cc., diluted with H2O, the organic layer dissolved in Et2O, the solution washed twice with 5% aqueous Na2CO3, extracted with two 20-cc. portions of cold 10% aqueous KOH, and the alk. extract refluxed 2 hrs. and then acidified gave 1.2 g. (30%) pure I, m. 290-1° (from aqueous AcOH)(all m.ps. are corrected). The Et2O solution evaporated, the residue refluxed 6 hrs. with 40 cc. 10% alc. KOH, and the mixture acidified gave a mixture of the cis (III) and trans (IV) isomers of 4-(4-hydroxycyclohexyl)benzoic acid, m. 167-73°. The mixture dissolved in 15 cc. warm N aqueous NaOH, treated with 6 g. NaNO3 in 10 cc. H2O, cooled, filtered, and the filter cake washed with a small amount of cold H2O, dissolved in 10 cc. hot H2O, and acidified gave 0.29 g. (10%) IV, m. 228.5-34.5° [analytical sample, m. 235-7° (from Me2CO)]; the filtrate from the IV acidified gave 1.31 g. (45.5%) III, m. 175-87° [analytical sample, m. 194.0-5.7° (from Me2CO)]. I (2.14 g.)in 1.5 g. KOH and H2O and 3 cc. W-5 Raney Ni diluted with H2O to 31 cc., the mixture hydrogenated as before, filtered, and acidified gave 1.9 g. acids, m. 175-200°; the acids in 15 cc. warm N NaOH treated with 5 g. NaNO2, the mixture cooled, the precipitate dissolved in hot H2O, and the solution acidified gave 0.65 g. (42.5%) IV, m. 230-5°; the filtrate acidified yielded 1.15 g. mixture of I and III, which was fractionally crystallized from Me2CO to yield 0.45 g. (29.4%) III, m. 187-93°; the mother liquor evaporated to dryness and the residue recrystallized from dilute AcOH yielded 0.65 I, m. 285-91°. The hydrogenation of 4.0 g. I with 3-months old W-2 Raney Ni under the same conditions 4 hrs. yielded 1.27 g. (37.5%) IV, 0.63 g. (18.6%) III, and 0.7 g. I. III (0.22 g.) heated 6 hrs. on the steam bath with 3 cc. glacial AcOH saturated with HBr, the solution poured into 30 cc. cold. H2O, extracted with 20 cc. CHCl3, the extract washed with H2O, dried with MgSO4, evaporated, the residue dissolved in 30 cc. MeOH containing 0.06 g. Na, hydrogenated 3 hrs. over 3 cc. Raney Ni at 40 lb. initial pressure, the mixture filtered, the filtrate evaporated to dryness, the residue dissolved in H2O, acidified with excess concentrated HCl, and heated on the steam bath, and the precipitate recrystallized from petr. ether and dilute EtOH gave 4-cyclohexylbenzoic acid (V), m. 195-6°. IV (0.22 g.) gave similarly 130 mg. (64%) V. IV (0.22 g.) in 5 cc. glacial AcOH treated dropwise during 1 hr. with stirring with 0.138 g. CrO3 in 14 cc. H2O and 0.7 cc. AcOH, the mixture stirred 2 hrs., treated with 2 cc. MeOH, poured into 150 cc. H2O containing 5 cc. concentrated HCl, extracted with 30 cc. CHCl3, and the extract washed with H2O, dried, and evaporated gave 180 mg. (82.5%) 4-(4-oxocyclohexyl)benzoic acid (VI), m. 227.5-30.5°. III (0.275 g.) yielded similarly 204 mg. (74%) VI, m. 228-31°. I (4.0 g.), 2.1 g. KOH in H2O, and 4 cc. W-5 Raney Ni diluted to 31 cc. with H2O, and the mixture hydrogenated 10 hrs. at 150° and 2500 lb. pressure gave similarly 2.3 g. (54.5%) 4-(4-hydroxycyclohexyl)cyclohexanecarboxylic acid (VII), m. 173.7-4.7° (from Me2CO). VII (0.5 g.) heated 7 hrs. on the steam bath with 5 cc. glacial AcOH saturated with HBr, the solution poured into H2O, the oily solid extracted with 100 cc. CHCl3, the extract washed with H2O, dried, evaporated, the residual oil in 50 cc. MeOH containing 0.2 g. Na and 3 cc. Raney Ni hydrogenated 6 hrs. at 40 lb. initial pressure, the mixture filtered, evaporated to dryness, the residue dissolved in H2O, the solution acidified, the precipitate extracted with two 50-cc. portions Et2O, the extract washed, dried, evaporated, and the residue crystallized from petr. ether gave 350 mg. (76.9%) trans-4-cyclohexylcyclohexanecarboxylic acid, m. 159-60° (from petr. ether); amide, m. 199-200°. VII (0.5 g.) in 9 cc. glacial AcOH oxidized similarly with 0.41 g. CrO3 in 0.4 cc. H2O and 0.9 cc. AcOH yielded 350 mg. (70.8%) trans-4-(4-oxocyclohexyl)cyclohexanecarboxylic acid, m. 174-6.5° (from pert. ether). p-BrC6H4OMe (200 g.) in 350 cc. dry Et2O added dropwise to 26 g. Mg in 200 cc. dry Et2O containing 1 cc. purified EtI at such a rate as to keep the mixture gently refluxing, the mixture refluxed 1 hr., cooled, treated rapidly with stirring with 180 g. 3-methylcyclohexanone in 200 cc. dry Et2O, stirred 1 hr., decomposed with excess cold N H2SO4, the Et2O layer washed with H2O, dried, distilled, the residue dissolved in 200 cc. glacial AcOH, added to 10 cc. Ac2O and 2 g. 2-C10H7SO3H, the mixture refluxed 1 hr., poured into H2O, extracted with 500 cc. Et2O, and the extract dried and fractionated gave 147 g. (65.5%) impure 4-methoxy-3′-methyl-3′,4′,5′,6′-tetrahydrobiphenyl (VIII), b6 144-6°. VIII (145 g.) heated with 28.25 g. S at 225°, the temperature gradually raised during 3.5 hrs. to 240°, the mixture cooled, the hard red solid dissolved in Et2O, the solution evaporated, and the residue distilled gave 116.7 g. (81%) m-(p-MeOC6H4)C6H4Me (IX), pale yellow distillate, b4 139-41°, which crystallized from dilute EtOH in colorless plates, m. 51-2°. IX (40 g.) in 800 cc. pyridine and 800 cc. H2O heated with stirring on the steam bath, the mixture treated during 3.5 hrs. with 127 g. KMnO4 in portions, filtered, the MnO2 digested on the steam bath with 300 cc. 50% aqueous Me2CO, the combined filtrates concentrated to 600 cc., washed with 500 cc. Et2O, cautiously acidified to Congo red with concentrated HCl, and the precipitate recrystallized from dilute AcOH gave 24 g. (97%) m-(p-MeOC6H4)C6H4CO2H (X), m. 202-3°; evaporation of the Et2O washing yielded 18 g. IX. X treated with excess CH2N2 gave the Me ester, m. 70-1.5° (from petr. ether). X (20 g.) refluxed 13 hrs. under N with 250 cc. glacial AcOH and 75 cc. 48% HBr, the solution concd, to 0.5 volume in vacuo, diluted with H2O, cooled, and the solid deposit recrystallized from dilute AcOH gave 16.5 g. (88%) II, m. 241-2°. II (2.46 g.), 0.85 KOH, and 3 cc. W-5 Raney Ni diluted with H2O to 31 cc., hydrogenated 1 hr. at 75° and an initial pressure of 2500 lb., the mixture filtered, the filtrate acidified, extracted with Et2O, the residue from the extract esterified with 100 cc. MeOH and 2 cc. concentrated H2SO4, and the phenolic and nonphenolic fractions separated and processed as described for I yielded 1 g. II and 1.6 g. (63.5%) m-(4-hydroxycyclohexyl)benzoic acid, m. 150-1.8° (from Et2O-hexane); the similar hydrogenation of II in 1 equivalent aqueous Na2CO3 gave the same yield of the hexahydro derivative
Journal of the American Chemical Society published new progress about 20029-52-1. 20029-52-1 belongs to quinuclidine, auxiliary class Carboxylic acid,Benzene, name is 4-Cyclohexylbenzoic acid, and the molecular formula is C13H16O2, Product Details of C13H16O2.
Referemce:
https://en.wikipedia.org/wiki/Quinuclidine,
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