74 



ALCOHOLS 



[19 A-B. 



SYNTHETICAL PROCESSES. 



[A.] From acetic acid [Vol. II] and 

 methyl alcohol [13] through the com- 

 pound formed by the interaction of 

 zinc methyl and acetyl chloride and 

 decomposition of this compound by 

 water (Butleroff, Jahresber. 1864, 496 ; 

 Ann. 144, i ; Wagner and Saytzeff, 

 Ann. 175, 361 ; Pawloff, Ann. 188, 

 1 1 8). The same intermediate com- 

 pound is formed from zinc methyl and 

 carbonyl chloride (Butleroff, Zeit. 1863, 

 484). Magnesium methyl and acetyl 

 chloride can be used also in this syn- 

 thesis (Fleck,, Ann. 276, 129). Or 

 magnesium methiodide and methyl 

 acetate (Grignard, Comp. Rend. 132, 

 336), or magnesium methiodide and 

 acetyl chloride (Tissier and Grignard, 

 Ibid. 683). 



Or from dichloracetic acid through 

 dichloracetyl chloride (Otto and Bec- 

 kurts, Ber. 14, 1618), 'which, by inter- 

 action with zinc methyl and decompo- 

 sition of the product with water, gives 

 dimethylisopropyl carbinol (Bogomo- 

 letz, Ann. 209, 82). Subsequent steps 

 through pinacone, pinacolin, trimethyl- 

 acetic acid, &c., as below under D 

 and E. 



Isobutylene is among the products 

 formed by dropping acetic acid on to 

 heated zinc chloride (LeBel and Greene, 

 Am. Ch. Journ. 2, 26). 



[B.] From isobutyl alcohol [is] 

 through isobutylene by heating with 

 sulphuric acid (Lermentoff, Ann. 196, 

 1 17 ; Puchot, Ann. Chim. [5] 28, 508 ; 

 Comp. Rend. 85, 757 : for use of zinc 

 chloride as a dehydrating agent see 

 Nevole, Bull. Soc. [2] 24, 122: see 

 also Konowaloff, Ber. 13, 2395; Bull. 

 Soc. [2] 34, 333, and Scheschukoff, 

 Journ. Russ. Soc. 16, 510 : with the 

 ordinary dehydrating agents, Konowa- 

 loff, loc. cit. ; LeBel and Greene, Bull. 

 Soc. [2] 29, 306, or with heated plum- 

 bago crucible material as pyrogenic 

 contact substance, Ipatieff, Ber. 35, 

 1061, pseudobutylene is also formed : 

 see further Faworsky and Desbout, 

 Journ. pr. Ch. [2] 42, 152 ; Ipatieff, 

 loc. cit. : for production of isobutylene by 

 passing the vapour of the alcohol mixed 



with air over heated platinum see 

 v. Stepski, Monats. 23, 773). Iso- 

 butylene is formed also by the action 

 of alcoholic potash on isobutyl iodide 

 (Butleroff, Ann. 144, 19; Zeit. [2] 

 6, 278 : see also De Luynes, Comp. 

 Rend. 56, 1175; Ann. Chim. [4] 

 2 > 385) or chloride (Nef, Ann. 318, 

 28). Isobutylene on treatment with 

 sulphuric acid and hydrolysis gives 

 tertiary butyl alcohol (Butleroff, Ann. 

 144, 22 ; 180, 246) ; or by combina- 

 tion with zinc chloride it forms a crys- 

 talline compound which yields tertiary 

 butyl alcohol on decomposition with 

 water (Kondakoff, Journ. Russ. Soc. 

 25, 345 and 456 ; also Journ. pr. Ch. 

 [2] 54,442). Isobutylene is converted 

 into tertiary butyl alcohol by the action 

 of aqueous oxalic acid (Miklaschewsky, 

 Journ. Russ. Soc. 22, 495). On com- 

 bination with hydrogen iodide iso- 

 butylene gives tertiary butyl iodide 

 (Butleroff, Ann. 144, 22 ; Markowni- 

 koff, Zeit. [2] 6, 29), which can be 

 converted into the alcohol by the action 

 of water (Scheschukoff, Bull. Soc. [2] 

 45, 181 ; Dobbin, Trans. Ch. Soc. 37, 

 238). 



Isobutyl iodide on treatment with 

 acetic acid and silver oxide gives also 

 tertiary (with isobutyl) alcohol (Linne- 

 mann, Ann. 162, 12; Butleroff, Ann. 

 168, 143). 



Isobutyl alcohol can also be con- 

 verted into isobutyl chloride by the 

 action of hydrogen chloride, and then 

 into isobutylene by the action of 

 aluminium chloride on isobutyl chloride 

 (Mouneyrat, Ann. Chim. [7] 20, 485). 



Also from isobutyl alcohol through 

 isobutylamine by the action of ammonia 

 on the iodide or bromide (Reimer, Ber. 

 3, 756 ; Hughes and Romer, Ber. 7, 

 511) or chloride (Malbot, Bull. Soc. 

 [2] 47, 957 ; [3] 4, 693 ; Comp. Rend. 

 104, 63 ; 228) and the action of nitrous 

 acid on isobutylamine (Linnemann, 

 Ann. 162, 24). Isobutylamine can also 

 be obtained from the alcohol by heat- 

 ing with ammonio-zinc chloride (Merz 

 and Gasiorowski, Ber. 17, 623). Ter- 

 tiary butyl alcohol is obtained also from 

 isobutyl iodide through the cyanate 

 (Brauner, Ber. 12, 1874) and the action 



