B. B. FRENCQAND A. B. SCHAIEFER
1576 Summary
1. Reactions have been carried out between isobutyl bromide and aqueous solutions of various metallic hydroxides, Varying conditions of temperature and concentration. 2 . Yields of olefin varying from 10.8 to 65.5% have been obtained.
[CONTRIBUTION FROM THE CHEMICAL
1701. 57
3 . The formation of olefin is favored by higher temperatures and higher concentrations of alkali. 4. The rate of reaction is greater in the dilute so~utions. 5 . Rearrangement of the isobutyl bromide t o the tertiary bromide does not take place during these reactions. COLUMBIA,
Mo.
LABORATORY O F THE
RECEIVED MAY8, 1935
UNIVERSITY OF MISSOURI]
Action of Inorganic Bases on Tertiary Amyl Halides’ BY H. E. FRENCH AND A. E. SCHAEFER TABLE I In earlier publications2 it was noted that, in METHODS OF SYNTHESIS OF TERTIARY AMYLHALIDES general, the action of dilute aqueous solutions of B. p. of halide Yield, metallic hydroxides on the butyl bromides causes Reagent OC. Mm. naOD % 85-88.5 1.4023 increasing yields of olefin as the temperature of Acetyl chloridea Phosphorus trichlorideb 83-84.5 740 1.4048-1.4049 4 0 . 8 reaction is increased and as the concentration of Thionyl chloride’ 83-84.5 744 1.4048-1.4049 41.1 83-84 744 1.4047-1.4048 18.2 the alkali is increased. The different isomers Oxalyl chlorided Concd. HCle 83-85 1.4046-1.4047 were found t o follow these generalizations in 48% HBr’ 65-68 194-196 1.4411 46-49 152 1.4410 varying degree, with the tertiary butyl bromide HBr gas0 53-55 151 1.4420 forming but little olefin under any of the condi- HBr gas -P trimethylethyleneh 56-57.5 152 1.4421 65 tions used. In decided contrast to this is the bePhosphorus ttibrornide 57-58 152 1,4420 35 havior of the corresponding tertiary butyl chlonZoD for the chloride 1.4056, for the bromide 1.4421, ride, which was found by Woodburn and Whit- “International Critical Tables,” Vol. I, p. 277. more3 to yield only olefin in hot solution, and Henry, Rec. frav. chim., 26, 89 (1906). Product dried chiefly olefin with cold solutions of alkalies. The over calcium chloride. present paper is concerned with the action of diWischnegradsky, Ann., 190, 328 (1878). Product lute aqueous solutions of alkalies on the tertiary dried over anhydrous potassium carbonate, then over calcium chloride. amyl bromide and chloride. Clark and Streight, Trans. Roy. SOC. Can., 23, series 3, Reagents, Apparatus and Procedure.-The 77 (1929). Product dried over anhydrous potassium cartertiary amyl alcohol used in this work was the bonate then over phosphorus pentoxide. best grade obtainable from the Eastman Kodak dAdams and Weeks, THISJOURNAL, 38, 2518 (1916). Company. Before use it was dried over lime and Product dried over phosphorus pentoxide. Eastman Kodak Company preparation. fractionally distilled through a 75-cm. column. I Norris, Watt and Thomas, THISJOURNAL, 38, 1076 The fraction boiling between 100.8-101.8° (731 (1916). mm.), n Z 51.4022, ~ was used. Faworsky, Ann., 354, 348 (1907). The tertiary amyl halides were prepared by Olefin prepared from tertiary amyl alcohol and sulfuric several different methods, a summary of which is acid. Norris and Reuter, THISJOURNAL, 49, 2630 (1927). given in the following table. At least two runs Preparation of halide, Wischnegradsky, Eoc. tit. were made with each method reported. formation of low boiling fractions which gave the Reduced pressures were found necessary in all von Baeyer test for olefins. In the process of puridistillations of the tertiary amyl bromide, since fication the chlorides were washed with ice water decomposition took place whenever distillation and dried over calcium chloride, anhydrous potaswas attempted a t atmospheric pressure, with the sium carbonate or phosphorus pentoxide. The ( 1 ) I hi, p a p r AIJ r h t r a c t ,,I tire tht. ~ u i , i u i t t r ~I,y l Mr crude bromides were. treatetl with a n h y d r o u s potas%haelex L U pailia1 liilhlrrrtiit c)f the r w ~ t i i r r r u ~icbr ~ ~llir l~ ~ l r ~ ~ r c siuiii carbonate, and distillrtl in 7 1 ~ 110. ( ’I‘he wash 01 hl I h,,’tur 01 Pt,il,>wytiq tit I lie I ,.!I i I lrriacti hIc\ti.iii arirl J d i l c r I n ; \ I I K C Y A I 66 I 4 1 , iiig with w a k r was omitted siiicr this trratiiirilL E
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