18 C-19.] 



ISOBUTYL ALCOHOL 



73 



the dry distillation of calcium isovalerate 

 (Dilthey, Ber. 34, 3115). 



Also from this acid by oxidation with 

 alkaline permanganate to /3-hydroxyiso- 

 valeric acid [(CH 3 ) 2 : C(OH) . CH 2 . 

 COOH] (v. Miller, Ann. 200, 273), /3- 

 dimethylacrylic acid [(CH 3 ) 2 : C : CH . 

 COOH] by distillation with dilute sul- 

 phuric acid (Neubauer, Ann. 106, 62 ; 

 v. Miller, loc. cit. 261), conversion into 

 isobutylene by heating to 210-220 

 (Gorboff and Kessler, Bull. Soc. [2] 41, 

 392), and then as under A. 



/3-Hydroxyisovaleric acid is also con- 

 verted into /3-dimethylacrylic acid (ethyl 

 ester) by the action of phosphorus tri- 

 chloride on ethyl /3-hydroxyisovalerate 

 (Semljanitzin and SaytzefP, Ann. 197, 

 72; Ustinoff, Journ. pr. Ch. [2] 34, 

 478 ; Bull. Soc. [2] 45, 255). Also 

 from isovaleric acid through the a- 

 bromo-acid (Borodin, Ann. 119, 1 22 ; 

 Cahours, Ann. Suppl. 2, 78 ; Fittig and 

 Clark, Ann. 139, 199; Ley and Popoff, 

 Ann. 174, 63) and the action of sodium 

 ethylate or ammonia on a-bromisovaleric 

 ester (Duvillier, Comp. Rend. 88, 913; 

 1209; 112, 1012; Ann. Chim. [5] 19, 

 428; Bull. Soc. [3] 5, 848) : /3-dimethyl- 

 acrylic acid is one of the products formed 

 and can be converted into isobutylene 

 as above. 



Ethyl /3-dimethylacrylate is obtained 

 by the action of diethylaniline or of 

 quinoline on a-bromisovaleric ester 

 (Weinig, Ann. 280, 253; W. H. Perkin, 

 junr., Trans. Ch. Soc. 69, 1471). 



[D.] From acetone [106] and glycerol 

 [48] by converting the latter into allyl 

 iodide (Berthelot and De Luca, Ann. 

 Chim. [3] 43, 258 ; Tollens, Bull. Soc. 

 [2] 9, 396 ; Glaus, Ann. 131, 59 ; 

 Oppenheim, Ann. Suppl. 6, 354 ; 

 Tollens and Henninger, Ann. 156, 

 156; Wagner, Ber. 9, 1810; Kanon- 

 nikoff and Saytzeff, Ann. 185, 191 ; 

 James, Ann. 226, 206 ; Behal, Bull. 

 Soc. [2] 47, 875 j Malbot, Ann. Chim. 

 [6] 19, 355 and 363), and allow- 

 ing zinc to act upon a mixture of 

 acetone and allyl iodide so as to form 

 dimethylallyl carbinol [CH 2 : CH . CH 2 . 

 C(CH 3 ) 2 .OH] (Saytzeff, Ann. 185, 

 151 and 175); oxidation of the latter 

 to /3-hydroxyisovaleric acid (Saytzeff, 



Ann. 185, 163 ; Schirokoff, Journ. 

 pr. Ch. [2] 23, 206); then to /3-di- 

 methylacrylic acid and isobutylene as 

 under C. 



A mixture of acetone, malonic acid, 

 and acetic anhydride gives dimethyl- 

 acrylic acid on heating (Massot, Ber. 

 27, 1225). Acetone and acetoacetic ester 

 condense under the influence of hydro- 

 gen chloride to form isopropylidene- 

 acetoacetic ester, and this on boiling 

 with barium hydroxide solution yields 

 dimethylacrylic acid (Pauly, Ber. 30, 

 481). ' 



Also from acetone and acetic acid by 

 converting the latter into chloracetic 

 ethyl ester (Willm, Ann. 102, 109 ; 

 Conrad, Ann. 188, 218) and allowing 

 zinc to act upon a mixture of acetone 

 and the ester so as to form ethyl /3- 

 hydroxyisovalerate (Ref ormatsky, Journ. 

 Russ. Soc. 22, 47), which can be hydro- 

 lysed and treated as above. 



The ' acetone-chloroform ' referred to 

 under tertiary butyl alcohol [19 ; D] 

 gives isobutylene on boiling with alco- 

 hol and zinc dust (Jocitsch, Journ. 

 Russ. Soc. 30, 920; Ch. Centr. 1899, 

 1, 606). 



[E.] Isobutyric aldehyde [94] gives 

 isobutyl alcohol (with isobutyric acid) 

 on heating with barium hydroxide 

 solution (Lederer, Monats. 22, 536). 



19. Tertiary Butyl Alcohol ; 

 Trimethyl Carbinol ; 

 2 - Methyl- 2-Pr opanol. 



CH 3 .C(CH 3 )(OH).CH 3 



NATURAL SOURCE. 



Has been said to occur in small 

 quantity in certain fusel oils (Rabuteau, 

 Comp. Rend. 87, 501 ; Butleroff, Ann. 

 144, 34; Trommsdorf, as quoted by 

 Meyer and Jacobson, <Lehrb. d. org. 

 Ch/ p. 161). It is probable, however, 

 that the alcohol thus obtained was 

 formed from isobutyl alcohol during 

 the process of treatment (Meyer and 

 Jacobson, loc. cit.}. 



