1654
G. E. MCCASL.AND AND E. CLYDEHORSWILL
Vol. 76
pine, Pinus densifEora, Sieb. and Zucc., and supplied to us ether proved to be slightly impure isolongifolol (0.3 g.) by the Arakawa Forest Products Company of Osaka, Japan. which further cryztallization failed t o improve: m.p. 107The sesquiterpene was distilled from sodium before use and log", [ a ]-45.0 ~ . fraction 2 (0.2 g.), m . p . 63-66", [ a ] ~ had the following constants: b.p. 144-146' (30 mm.), -23.5", and fraction 3 (0.3 g.), tr1.p. 63-70", [ a ] D--29.2', n Z 5 ~1.5000, a Z 5 +38.14'; ~ hydrochloride, m.p. 5X.k also were not improved by recrystallization. The infrared 59.5', [CY]"D +9.S0 (in CHCla); hydrobromide, m.p 69 . spectra of the three first fraction isolongifolols were identical, Simonsens reports these constants for longifolene obtained and those of fractions 2 and 3 from the reduction of cu-longifrom Indian terpentine oil: b.p. 150-151° (36 mm.), Z30D folic acid were very similar to t h a t spectrum of isolongifolol. 1.495, CYD +42.73'; hydrochloride, m.p. 59-60', [ a ] D Longifolene from Isolongifolo1.-Pure isolongifolol (2.0 +7.1" (in CHC13); hydrobromide, m.p. 69-70'. g.) was dissolved in 50 ml. of anhydrous ether and 2.0 g. Longifolene hydrobromide was dehydrobrominated in of phosphorus pentachloride was added. \\:bile the mixture 10% alcoholic potassium hydroxide a t reflux for 11 hr. to stood for 36 hours a t room temperature the solid peritachlolongifolene. The hydrochloride was considerably more reride lying initially at the bottom of the flask slowly dissistant to this treatment. solved. The clear solution was poured into water, and the Annl. Calcd. for C15Hz4: C, 88.16; H, 11.84. Found: ether layer was removed. This ether layer was washed with \vater, then with dilute sodium hydroxide solution, again C, 88.12; H, 11.51. \T ith water and finally dried over sodium sulfate. EvaporaThe Longifolic Acids.-Longifolene was oxidized and ozontive distillation of the residue, remaining after evaporation ized according t o the procedures of S i i n ~ n s e n . ~ ~Discrepant B values are given: longifolic acid, [a111+5.6" (opt. i n a ~ t . ~ ) ;of ether, at 100" (1 mm.) gave 0.2 g. of longifolene, [ a ] D +36.2", whose infrared spectrum was superimposable upon neut. equiv., 233, 234 (Cl6Hz4O2requires 236) ; isolongifolic t h a t of the sesquiterpene described above. If the ether acid, neut. equiv., 236, 236; a-longifolic acid, neut. equiv., solution of the reaction product is concentrated, a white 239, 239.5. The Longifolo1s.-Methyl isolongifolate (3.2 g . ) , m . p . crystalline substance is deposited, m.p. 121-123', as major product, and this material, which gave a positive phosphate 54-53' (54-55°),g was reduced in ether with excess lithium test, is believed to be the phosphate ester of isolongifolol. aluminum hydride. After working up in the usual manner, Isomerization of Longifo1ene.-Longifolene (10 9.) , [ a ] ~ the crude alcohol was crystallized from petroleum ether, was added to 20 ml. of sulfuric acid, 50 ml. of aceyielding 2 . 8 g. of pure isolongifolol, m.p. 111-112°, [ c Y ] ~ ~ +33.7", D - 46.9". Similar reduction of isolongifolic acid gave the tic acid and 70 ml. of water. This mixture was maintained a t ca. 80" on the steam-bath for 14 days, during which time same product. aliouots were withdrawn for rotation and infrared measureA n n l . Calccl. for C15EIzcO:C, 81.02; €1, 11.79. Found: ments. Specific rotation changes were: +33.7' (0 days), C, 80.98; H,11.38. t 2 1 . 1 ' ( l ) , f10.1" (2), +1.8' (3), -3.9" (4), -7.2' Reduction of longifolic acid (3.0 9.) yielded 1.6 g. of crudc (j),-9.6" (6), -15.4' ( 8 ) , -15.7' (9), -15.0' ( l l ) , alcohol, m.p. 50-90'. Crystallization of this material from -16.5" 114). petroleum ether gave as fraction 1, isolongifolol (0.46 g.), The isomerized product, p-longifolene, decolorized perm.p. 111-112', [ a ]-46.4'; ~ as fraction 2, crude longifolol, manganate solution and bromine in carbon tetrachloride. m.p. 75-80 , whose m.p. became constant a t $8.5-80.5' Anal. Calcd. for C15H84: C, 88.16; H , 11.84. Found: after two recrystallizations from the same solvent: 0.21 g., C, 87.72; H , 11.80. [ a ]+23.5". ~ Dehydration of Isolongifolo1.-Isolongifolol (1.3 9.) was A n a l . Calcd. for C I ~ H ~ ~C,O81.02; : H, 11.79. Found: heated with 0.9 g. of freshly fused potassium bisulfate beC , 81.03; H, 11.52. tween 220-230' for 1.5 hours. The product was extracted The reduction of a-longifolic acid (1.49.) gave 1.1 g. of with ether, washed and dried. Evaporative distillation a t crude alcohol, m.p. 57-90". Fraction 1 from petroleum 100' (1 mm.) yielded 0.5 g. of colorless, liquid hydrocarbon, -~ [ a ] D -62.6'. (8) J. I.. Simonsen. J , Citein. S o r . , 117,570 (1920). ( 0 ) Value reported b y J. I.. Simonsen.
[ COXTRIBLTIOS FROM
Cyclitols. VI.
XEWHAVEN. CONNECTICUT
THE DEPARTMENT O F CHEMISTRY, UNIVERSITY O F TORONTO]
A New Tetrol and Enediol from Cyclohexadiene-1,4 by the Prevost Reaction1 BY G. E. ~ICC.ISL.AND AND E. CLYDSHORSWILL~ RECEIVED XOVEMBER 5, 1953
Cyclohexadicne-l,3 i n excess reacts with silver iodine dibenzoate t o give trans-cyclohexenediol-3,~dibenzoate, which can be saponified to tra~ts-cyclohexenediol-4,5. The diene in deficiency reacts to give cyclohexanetetrol-l,2,4,5tetrabenzoate (m.p. 1 8 l 0 ) , which on arnmotiolysis gives a new cyclohexanetetrol-l,2,4,5of m.p. 208". Acetylation of the tetrol gives a tetraacetate of m.p. 148" The benzoylation of cyclohexeticdiol-3,4 is described. New Prevost reaction products of cyclohexene are reported.
Continuing our investigations 011 cyclitol cheniistry,' we wish to report the synthesis of a new cvclohexanetetrol 111 and a new cyclohexenediol V. The cyclohexanetetrols are of interest because of their close relationship to the naturallv occurring betit01,~quercitols and inositols. CyclohexenediolI I ) For previous (iinnumhered) papers in thi? series, see G. R . IlcCaslanrl and I?. Clvtle Horswill, T i r r s J O I J R X I I . . 75, -1020 (10JR). and references there r i t e i l . f 2 ) Fellow of t h r N:rtion:il Research Criiuicil, l!i>2 - 1 9 5 3 ( 3 ) n e t i t n l , :L de=tromtntnry crcl~,hexanetetri,l. was isolxte
