CALVINL. STEVENS AND BERNARD T. GILLIS
3448
Vol. 79
hydrogen was consumed and on fractional distillation, 65 g. (877,), of cis-2-carbethoxycyc1ohexano1, b.p. 125-217' (27 ~ (lit.3 117-118" (17 mm.)). mm.), n Z 61.4585
these derivatives, m.p. 133.5-134 (lit.9 134'). The monop-nitrobenzoate, previously unreported, also was isolated, m.p. 95-96", Anal. Calcd. for C14H1705Pi: C, 60.28; H, 6.14; X , Anal. Calcd. for C~H1603: C, 62.76; H, 9.36. Found: 5.02. Found: C, 59.60; H, 6.03; S, 5.00. C , 62.94; H, 9.47. Preparation of trans-2-Carboxycyclohexanol.-The mother Preparation of cis-2-Carboxycyclohexanol.-A mixture liquors from the preparation of cis-2-carboxycyclohexanol of 14.5 g. (0.08 mole) of 2-carbethoxycyclohexanol (95% were concentrated in vacuo and refluxed with 7.5 2%' potasczs) and 45 ml. of 257, aq. sodium hydroxide \vas stirred for sium hydroxide. The mixture was cooled, acidified to 12 hr . The sodium salt of cis-2-carbouycyclohexanol acid congo red with sulfuric acid and saturated with ammonium separated and was filtered. I t was dissolved in a small sulfate. The aqueous solution was extracted several times amount of water and the solution made acid to congo red with ether. The trans-acid was recrvstallized from eth! 1 with 10y0 hydrochloric acid. The aqueous solution was acetate, m.p. 109-1110 (iit.3 m.p. 111"). saturated with ammonium sulfate and extracted with ether. In a similar epimerization 12.1 g. (0.072 mole) of sodium The ether-soluble material was recrystallized from a small cis-cyclohexanol-2-carboxylate was transformed into the :mount of ether to give 5.4 g. (44Y0) of the cis-acid, m.p. trans-acid by refluxing with base. The yield was 5.6 g. 19-80' (lit.a 80-81'). (54'30) of pure trans-acid. Preparation of cis-2-Carbomethoxycyclohexanol.-To d Preparation of trans-2-Carbomethoxycyc1ohexano1.cooled solution of 5.1 g. (0.035 mole) of cis-2-carboxycyclo- The procedure was identical t o t h a t used for the cis-ester. hexanol in 25 ml. of ether was added an ether solution of Fractional distillation yielded a quantitative amount of thc Fractional distillation gave a quan- trans-methyl ester, b . p . 99.8-101.8' (2 mm.), m.p. 34-35', diazomethane a t 0-5'. titative yield of the desired ester, b.p. 87.5-88.5' (3 m m . ) , n Z 51.4632. ~ n Z 5 D 1.4647 ( l k 3b.p. 105' (14mm.), X Z 5 D1.4645). Preparation of trans-2-Hydroxymethyl-1-hydroxycycloPreparation of cis-2-Hydroxymethyl-1-hydroxycyclohex- hexane.-The procedure was identical to that used t o preane.-To a solution of 1.44 g. (0.038 mole) of lithium alumi- pare the cis-diol above. -4solution of 1.3 g . (0.032 mole) num hydride in 100 ml. of anhydrous ether, we added 5.4 g. of lithium aluminum hydride in 100 ml. of ether was used to (0.034 mole) of cis-2-carbomethoxycyclohexanol in an equal reduce 4.54 g . (0.029 mole) of trans-2-carbomethoxycyclovolume of ether a t such a rate as t o maintain slow refluxing. hexanol. Fractional distillation yielded 2.4 g. (63%) of
