19 B-H.] 



TERTIARY BUTYL ALCOHOL 



75 



of potash on the latter (Linnemann, 

 Ann. 162, 12). 



Also from isobutyl alcohol by heat- 

 ing- with hydrochloric acid and decom- 

 posing the tertiary chloride by heating 

 with water, the isobutyl chloride simul- 

 taneously formed remaining- undecom- 

 posed (Freund, Journ. pr. Ch. [2] 12, 



25)- 



Isobutyl alcohol, when converted into 



isobutylsulphuric acid and the barium 

 salt of the latter heated to 130, gives 

 a mixture of isobutylene (f) and pseudo- 

 butylene () (Biron, Journ. Russ. Soc. 

 29, 697). 



[C.] From isovaleric acid [Vol. II] 

 through isobutylamine by the action 

 of bromine and potash on the amide 

 (Hofmann, Ber. 15, 769) and then as 

 under B. Also from isovaleric acid 

 through isobutylene (see under isobutyl 

 alcohol [18; C]). 



[D.] From acetone [1O6] and glycerol 

 [48] through /3-dimethylacrylic acid 

 (see under isobutyl alcohol [18; D] 

 and isobutylene as above. Or from 

 acetone and acetic acid through (3- 

 hydroxyisovaleric ester and isobutylene 

 as under isobutyl alcohol [18 ; D]. 



Also from acetone and chloroform 

 [l; D] through ' acetone chloroform/ 

 CCl3.C(CH 3 )..OH (Willgerodt and 

 Genieser, Journ. pr. Ch. [2] 37, 364 ; 

 also Willgerodt, Ber. 14, 245 1 ; 16, 

 1585 ; Cameron and Holly, Journ. 

 Physical Ch. 2, 322), and reduction of 

 the latter with zinc and hydrochloric 

 acid at 100 (Willgerodt and Diirr, 

 Journ. pr. Ch. [2] 39, 287). 



Also in small quantity from acetone 

 and methyl iodide by the action of 

 sodium on the moist ethereal solution 

 (Frey, Ber. 28, 2520). Or to the ex- 

 tent of 70 per cent, from acetone by in- 

 teraction with magnesium methiodide 

 (Grignard, Ch. Centr. 1901, 2, 623). 



Or from acetone through pinacone 

 ( = tetramethylethylene glycol) by the 

 action of sodium (Fittig, Ann. HO, 25 ; 

 114, 54; Stadeler, Ann. Ill, 277; 

 Friedel, Ann. 124, 329 ; Bull. Soc. [2] 

 19, 289 ; Friedel and Silva, Ber. 6, 

 35 ; 267 ; Jahresber. 1873, 340 ; 

 Thiele, Ber. 27, 455), or by electro- 

 lysis (Merck, Germ. Pat. 113719 of 



1899; Ch. Centr. 1900, 2, 794), pin- 

 acolin (= dimethylbutanone) by dis- 

 tilling pinacone with dilute sulphuric 

 acid (Fittig, Ann. 114, 56 : see also 

 Vorlander, Ber. 30, 2266), trimethyl- 

 acetic = pivalic acid by the oxidation 

 of pinacolin (Friedel and Silva, Comp. 

 Rend. 77, 48; Reformatzky, Ber. 23, 

 1596). The acid gives trimethyl car- 

 binol when the potassium salt is electro- 

 lysed in aqueous solution (Petersen, 

 Zeit. physik. Ch. 33, 698). 



[E.] From isobutyric acid [Vol. II], 

 the calcium salt of which gives pin- 

 acolin on distillation (Barbaglia and 

 Gucci, Ber. 13, 1572), and then as 

 above. 



Or from isobutyric acid and methyl 

 alcohol through dimethylisopropyl car- 

 binol, which is formed by the inter- 

 action of isobutyl chloride and zinc 

 methyl and decomposition of the product 

 with water (Prianischnikoff, Zeit. [2] 

 7, 275). The tertiary hexyl iodide 

 corresponding to the alcohol on treat- 

 ment with alcoholic potash gives tetra- 

 methylethylene (Pawloff, Ann. 196, 

 124), and the bromide of the latter on 

 treatment with silver acetate and 

 hydrolysis yields pinacone (Ibid. 126). 

 Or the dimethylisopropyl alcohol gives 

 tetramethylethylene on distillation with 

 sulphuric acid (Reformatsky and Ples- 

 canossoff, Ber. 28, 2841). 



[F.] From amyl alcohol [22] and 

 methyl- alcohol [13] through trimethyl- 

 ethylene (see under acetone [106 ; E]), 

 which gives tetramethylethylene on 

 heating with lead and methyl iodide 

 at 220-230 (Eltekoff, Journ. Russ. 

 Soc. 14, 380). Subsequent steps 

 through pinacone as above. Or from 

 fusel oil amyl alcohol through iso- 

 butylene by pyrogenic decomposition 

 (see under isobutyl alcohol [18 ; B]) and 

 then as under B above. 



[G.] From ethyl [14] and methyl 

 alcohol [13] through chloral (Liebig, 

 Ann. 1, 1 89), which by interaction with 

 zinc methyl gives dimethylisopropyl 

 carbinol (Rizza, Journ. Russ. Soc. 14, 



99)' 



[H.] From propionic acid [Vol. II] 



and methyl alcohol [13]. a-Brompro- 

 pionic acid (Friedel and Machuca, Ann. 



