44 A-46 A.] 



METHYLACETYL CARBINOL 



95 



SYNTHETICAL PROCESSES. 



[A.] From dlacetyl [113] by reduc- 

 tion with zinc and dilute sulphuric 

 acid (v. Pechmann and Dahl, Ber. 23, 

 2421). 



[B.] From acetoacetic ester [Vol. II] 

 and methyl alcohol [13] through methyl- 

 acetoacetic ester by the interaction o 

 methyl iodide and sodio-acetoacetic ester. 

 The methylacetoacetic ester on hydroly- 

 sis gives methylefchyl ketone (Frankland 

 and Duppa, Ann. 138, 336; Booking-, 

 Ann. 204, 17), and this on chlorination 

 yields methyl-a-chlorethyl ketone (Vla- 

 desco, Bull. Soc. [3] 6, 408; 807). 

 The latter gives methylacetyl carbinol 

 on treatment with alcoholic sodium 

 hydroxide (Ibid. 810). 



[C.] From acetic and propionic acids 

 [Vol. II] through methylethyl ketone 

 by distilling a mixture of the calcium 

 salts (Schramm, Ber. 16, 1581). Sub- 

 sequent steps as under B. 



[D.] From acetic and butyric acids 

 [Vol. II] through methylethyl ketone 



by distilling a mixture of the calcium 

 salts (Grimm, Ann. 157, 258). 



NOTE : Other generators of methylethyl ke- 

 tone are : zinc methyl and propionyl chloride 

 (Popoff, Ann. 145, 289) ; sine ethyl and acetyl 

 chloride (Freund, Ann. 118, 3) or acetic anhy- 

 dride (Granichstadten and Werner, Monats. 32, 

 315) ; ethyl iodide and acetic anhydride in presence 

 of zinc-sodium alloy (Saytzeff, Zeit. [2] 6, 104^ ; 

 2 : 2-dibrombutane by heating with water or 2 : 3- 

 dibrombutane by heating with lead oxide and 

 water (HOlz, Ann. 250, 234 ; Eltekoff, Journ. 

 Russ. Soc. 10, 219 ; Meyer and Petrenko, Ber. 

 25, 3309) ; crotonylene by the action of sulphuric 

 acid (Lwoflf and Alme'dingen, Bull. Soc. [2] 37, 

 493) ; secondary butyl alcohol (methylethyl car bi nol ) 

 by passing the vapour over a heated platinum 

 spiral (Trillat, Comp. Rend. 132, 1495), or by 

 oxidation (Kanonnikoff and Saytzeff, Ann. 175, 



377). 



Methylethyl ketone is also obtained from the 

 generators of pseudobutylene, the latter giving 

 with hypochlorous acid a chlorhydrin which 

 yields the ketone on heating with water (Kras- 

 suski, Journ. Russ. Soc. 34, 287). Generators 

 of pseudobutylene are : n-propyl alcohol [15] 

 through hexane ; n-butyl alcohol [17] ; secondary 

 butyl alcohol,hom the n-alcohol through n-butyl- 

 ene and the secondary iodide ; isobutyl alcohol 

 [18] ; methyl alcohol [13] and glycerol [48] ; alde- 

 hyde [92] ; angelic and tiglic acids [Vol. II] ; 

 isovaleric acid [Vol. II] ; isoamyl alcohol [22], For 

 references see under secondary butyl isothio- 

 cyanate [165 ; A ; B ; C ; D, &c.]. 



POLYHYDBIC ALCOHOLS. 



45. Etliylene Glycol ; Ethauecliol, 

 CH 2 (OH).CH a (OH) 



NATURAL SOURCE. 



Said to be a product of oxidation of 

 glycerol by a micro-organism found in 

 wine (Rensch, Pharm. Zeit 39, 864). 



SYNTHETICAL PROCESSES. 



[A.] From ethyl alcohol [14] through 

 ethylene (see under isopropyl alcohol 

 [16 ; C]). 



NOTE : All generators of ethylene are thus 

 generators of glycol (see under methane [1 ; 

 D], and under ethyl alcohol [14 ; A ; G ; E ; 

 J;N;0;T;W;X;Y, &c.]). 



[B.] From choline [Vol. II] by boil- 

 ing the aqueous solution (Wurtz, Ann. 

 Suppl. 6, 200). 



46. Trimethylene Glycol ; 



Normal Fropylene Glycol ; 



1 : 3-Fropanediol. 



CH 2 (OH).CH 2 .CH 2 (OH) 



NATURAL SOURCES. 



A product of the bacterial fermenta- 

 tion of glycerol in presence of chalk 

 (Freund, Monats. 2, 638 ; Fitz, Ber. 

 15, 876). Fitz's organism was probably 

 Bacillus butylicus (see under n-butyl 

 alcohol [17]). Propylene glycol occurs 

 as a product of hydrolysis of the fats 

 used for soap manufacture (Noyes and 

 Watkins, Journ. Am. Ch. Soc. 17, 

 890). 



SYNTHETICAL PROCESSES. 



[A.] From glycerol [48] through ally! 

 bromide (n-propyl alcohol [15 ; E] ), 

 trimethylene bromide by combination 



