Cuts 1 and 2 appeared to be mainly terpinolene (I>. p 84’ (24 nim.) and nap, 1.4888) with some lower boiling terpenes. Cut 3 was identified a5 mainly a,a-dimethyl-Pniethylbenzylalcohol (b. p. 118’ (24mm.) andnND 1.5185)
Summary The primary product of terpinolene o x d -~ tion with molecular oxygen in a single liqui,i by the phenylurethan m. p. 119-20’ (lit. 118-119Oj. phase is a very unstable, iodine-liberating perox The highly oxidized oil also is made stable by hydrogenation prior to distillation. A 451-g. portion of oil N ~ S idic substance which cannot be reduced or decomposed to related simple compounds. irnoothly hydrogenated with 50 g. of Raney nickel catalyst ,tt temperatures from W-142°, 9.2 g. of hydrogen being 1. In the presence of an aqueous phase, large ,ii,sorhed Thr recovered oil, 470 g , w a i .t~..ini-di~tillcct .iitiounts (as high 3s 120 parts per 100 parts terping of rt.iitlut The r l i giving 121 p. of distillate and olene) of iwter-soluble products can he obt:ll,rte nab fr,tctlon:itcti mto 0 tained. The major constituents (about 10-4.5 7,” /%tiinin.,, ) I % 1.IPiX-1 4 I Ii 0 1I ul I yc i r IC .I lcoliol The 7t eain caii be recovered ) are three crystalline rnentheneili\tillcti givirig 7 0 1 g of tlihydric triols iiielting ,it t ~ ~ ~ ~ !?$‘ ‘ , :ind l ? l l ” , respw iiirii )-120° 3 0 r ! i i n i n iI lelx tivrly. ineric residuc , 3 . The estimated composition of the non-crys Dihydric Alcohol Cut. -.1 nd Calcti. for C, 4 4 d 3 j : C , 69.8; IX, 11.62. - 1 ~ a Calcd. for CioHiaO2: C, 7O.B, tallizing purtion of the water-soluble products in 13, 10.6 Found: c,F7!L ; H , 10.91; saponification no , typical case was about 16% monoesters (formates 40. This indicates lo , iono icetite of the dihydiic aland acetates) of menthenetriols, 18% dihydroxy cohol. ketones, 32c,& menthenediols, a n d an additional Polymeric Residue. -Fouiitl. C. 7.2 6 H, (4 i 7 , nioi :Nc { menthenetriols. 4. -4s by-products, water-immiscible “oxidized oils,” apparently containing menthadienols, iiien thenediols, and their esters, ketones,.and oxyi S iiionohyciric alcohol gen-containing dimers, ‘ire also recovered in xwy22 7 ilihydric ,i!coliol iiig dmounts. 111 x 1,olymt 1 I l l I;
10s.
1.
\ \ I 1 ~ ~ l \ ~ 7 1 0l )YF ,I A \ V \ R l
~~O*~TI
