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Aug. 5, 1953 PEROXIDES FROM TURPENTINE : PINANE HYDROPEROXIDE 3675 tals has indicated oxidation of the sulfur atoms.lS The above results are consistent with a mechanism involving (1) the consumption of three moles of periodate to cleave the contiguous hydroxyl bearing carbon chain to give two moles of formic acid and two of glyoxal diethyl mercaptal, (2) the consumption of four moles of periodate to give two moles of glyoxal diethyl sulfoxide, (3) the spontaneous decomposition of the latter to give two moles of formic acid and two of formaldehyde diethyl sulfoxide and (4) slow oxidation of the latter to formaldehyde diethyl sulfone.D-Mannohexodialdoee (VI) .-Diisopropylidene-D-mannohexodialdose ( 5 9.) was heated a t 100' for 40 minutes with 50% acetic acid (20 ml.) the solvent was removed by distillation, and the thick sirup obtained was dissolved in water ( 5 ml.). This solution was poured into absolute ethanol (50 ml.). The amorphous material that precipitated was collected and dried. It sintered at 150-160" and turned brown. The specific rotation a t 20" was +47.7" (c 1, water).Anal. Calcd. for CeHloOe: C, 40.3; H, 5.6. Calcd. for CsHloO6.0.5H20: C,38.5; H,5.9. Found: Ci38.9; H,5.9. D-Mannohexodialdose was not fermented by a bakers yeast that fermented D-mannose readily. 2,3-4,5-Diisopropylidene-~-mannitol (VII) . -A solution of I (1.0 8.) in water (25 ml.) was treated with 0.3 Msodium metaperiodate (15 ml.). After one hour most of the periodate (15) C. Huebner, R. Pankratz and K. P. Link, THIS JOURNAL, 71, 4811 (1950).had been consumed, and sodium borohydride (0.38 8.) was added to reduce the aldehyde groups. After one hour, the solution was extracted four times with chloroform (25 ml. each portion). .The combined chloroform extract was washed once with water (10 ml.), then the organic layer was concentrated to a thick sirup which began to crystallize. It was recrystallized from benzene, to give 2,3-4,5-diisopropylidene-D-mannitol (0.7 g.) with m.p. 90-92", and [(Y]l'D $13.4" (c 3, chloroform). Anal. Calcd. for C I~H~Z O~ (262): C, 55.0; H, 8.4. Found: C, 55.3; H, 8.4. Deacetonation of VI1 was accomplished by refluxing 0.25 g. in 0.5 N hydrochloric acid for five minutes. After removal of the solvent by distillation, the n-mannitol was crystallized from a mixture of water and ethanol. I t melted a t 164-165', and the m.p. was not depressed when the substance was mixed with authentic D-mannitol. The specific rotation, +29.4' (c 4.5), in the presence of two parts of sodium borate decahydrate, compares well with the literature value +28.6" (c 10) determined under similar conditions. Anal. Calcd. for CsHlaO6 (182): C, 39.5; H, 7.7.The preparation of cis-Z-pinane-2-hydroperoxide from j3-pinene is described. The @-pinene was converted to cis-l-pinane The cis-l-pinane was oxidized a t about 90" for 20 hours to give The pure cis-1-pinane-2-hydroperoxide was isolated by a comIts structure was proved by reduction to the known cis-pinanol- OLUSTEE, FLORIDAThis left 0.18 g. in the mother liquor.(15) L. M . Joshel, Ind. E...

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The oxidation of / -pinene, a constituent of turpentine, to pinonic and pinic acids has recently been investigated by this laboratory. The alkyl esters of these acids were found to be suitable for use in the synthetic lubricant and plasticizer field (1). Pinonic acid (I), a methyl keto monobasic acid, is readily prepared from alpha-pinene by oxidation with permanganate (2) or ozone. Its structure indicates that sz/m-homopinic acid (2,2-dimethylcyclobutane-l ,3diacetic acid) (II), a Cio dibasic acid, could be prepared from pinonic acid by the use of the Willgerodt reaction (3). Guha and Ganapathi (4, 5) prepared irans-sz/m-homopinic acid from czs-diethyl norpinate by reduction to the glycol, conversion of the glycol to the dibromide, thence to the dinitrile, followed by saponification to the acid.Esters of sz/m-homopinic acid should be valuable as synthetic lubricants and plasticizers. Because of its higher molecular weight and symmetrical nature, this acid should have some advantage over pinic acid in the preparation of plasticizers and synthetic fibers.

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