Trimolecular Acetone Peroxide in Isopropyl Ether

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:3. S o evidence that use of an optically ac- tive peroxide will cause an asymmetric synthe- sis in vinyl polymerization has been obtained. URBANA, ILLINOIS RECEIVED SEPTEMBER 3, 1942 Trimolecular Acetone Peroxide in Isopropyl Ether 131' FRED ACRL'E, JR., AND H. I,. HALLER During the past few years several notes have appeared in the literature citing explosions of isopropyl ether.l In all cases the ether had stood for several years and the explosion hazard was xttributed to the formation of peroxides. So far :is we have been able to learn, the responsible iwroside has not been isolated or described. Recently, while an organic compound was beiiifi crystallized from isopropyl ether,2 the mother liquor was evaporated on the steam-bath with the aid of a stream of air to about one-third of its original volume. On standing at room tempera- ture, a crop of crystals, resembling common salt, separated. They melted at 94". On recrystalli- zation from methyl alcohol the melting point was 9s'. The compound sublimed readily a t room temperature, liberated iodine from potassium iodide solution, and exploded on percussion or when heated on a platinum spatula. A molecular weight determination by the Signer method as modified by Clark3 gave a value of 221. The compound possessed all the properties of tri- molecular acetone peroxide,' and a mixture melt- ing point determination of the unknown peroxide with an authentic sample of trimolecular acetrme peroxide showed them to be identical. I rimolectilar acetone peroxide 'ivas readily ob- tained in crystalline form from four out of five lots of isopropyl ether, all of which gave qunli- tative tests for peroxides, when the ether was evaporated to one-third of its original volume on ithe steam-bath with a stream of air. The fifth ,. .11 ia) E. F. Degering, J . Chern. E d . , 13, 454 (1936); (b) B. 1.. (c ) G. T organ and R. H. Pickard, Chem. and Ind . , 66, 421 (15:3tji, !d C. Williams, J . SOC. Chem. I n d . , 66, 580 (1938). (2) The ether was a commercial grade that had stood in the I t was not Herrington, I n d . Eng. C'hem.. S e w s E d . . 20, 1458 (1942): laboratory in clear glass bottles for at least tive years. purified before use. 3, E. P. Clark, I n d , Ens . C h e w . , A n d . Ed.. 13. 320 f 1941) 4 I< X-n!ffcmtri i i . RVY , 28, 22G5 '1895! lot gave a viscous sirup from which no crystals of the trimolecular acetone peroxide were obtained. It is of interest to note that Radulesco5 found that the photochemical oxidation of isopropyl ether was slightly autocatalytic and produced acetone, water, peroxides, acids, and gum; and that Brown6 has shown the formation of acetone when the ether mixed with oxygen is passed over ii silver catalyst. Whether other peroxides are also present in isopropvl ether has not been deter- mined. Trimolecular acetone peroxide is pos- sibly responsible for the peroxide test found by Redemunn' with isopropanol. ( 5 ) G. Kadulesco, Ann. combusiible l iquides , 13, 1071 (1938,. (6) R. L. Brown, U. S. Patent 2,246,569, June 24, 1941. t7) L'. E. Kedemann, THIS JOURIVAL, 64, 3049 (1942). I:. S. DEPARTMENT OF AGRICULTURE :\GRICVI,rt'RAI, RESEARCH A1)MINISTRATIOK B U R E A U OF E N T O M 0 1 , O i ~ ~ ANI) PI,ANT Q U A R A N T I N E RELTPVII.LE, M n . R E C E I V E D APRIL 14, 1943 Some Fluorinated Compounds of Possible Chemotherapeutical Interest 1 i Y I