54 C-F.J 



BENZYL ALCOHOL 



109 



[C.] Benzoic acid [Vol. II] gives 

 benzyl alcohol on reduction with sodium 

 amalgam (Herrmann, Ann. 132, 76 ; 

 133, 335). 



Benzoyl chloride by reduction with 

 sodium amalgam in presence of hydro- 

 gen chloride, or by reduction with 

 sodium amalgam alone in moist ethereal 

 solution, gives benzyl alcohol (Lipp- 

 mann, Zeit. [2] 1, 700; Bull. Soc. [2] 

 4, 249 ; W. H. Perkin, junr., and Sud- 

 borough, Proc. Ch. Soc. 10, 216). 



The following synthetical products 

 are generators of toluene, and therefore 

 of benzyl alcohol under A : 



Generators of Toluene through Mesitylene 

 and Uvitic Acid. 



[D.] Acetone [103] on treatment with 

 sulphuric acid condenses to mesitylene 

 (Kane, Phil. Trans. 44, 474 ; Hofmann, 

 Journ. Ch. Soc. 2, 104; Cahours, Comp. 

 Rend. 24, 255 ; Varenne, Bull. Soc. [2] 

 40, 266 ; Fittig and Bruckner, Ann. 

 147, 42 ; Orndorff and Young, Am. Ch, 

 Journ. 15, 249 ; Meyer and Molz, Ber. 

 29, 283 1; Lucas, ibid. 2884; Kiister 

 and Stallberg, Ann. 278, 210 ; Noyes, 

 Am. Ch. Journ. 20, 807). Mesitylene 

 on oxidation with nitric acid gives uvitic 

 acid (Fittig and v. Furtenbach, Zeit. [2] 

 4, i ; Ann. 147, 295), and the latter on 

 distillation with soda-lime yields toluene 

 (Baeyer, Zeit. [2] 4, 119). 



[E.] Normal and isopropyl alcohols 

 [15 ; 16] through propylene (see under 

 glycerol [48 ; A]), propylene bromide, 

 allylene by the action of alcoholic potash 

 on the latter (Markownikoff, Ann. 118, 

 332 : see also Valentin, Ber. 28, 2664), 

 mesitylene by the action of sulphuric 

 acid on allylene (Schrohe, Ber. 8, 1 7 ; 

 Michael, Journ. pr. Ch. [2] 60, 441), 

 and then as under D. 



Or indirectly through propylene brom- 

 ide and cyanide, pyrotartaric acid by 

 hydrolysis of the latter (Simpson, Ann. 

 121, 161), and then through citrabrom- 

 pyrotartaric acid as under N and ally- 

 lene as under M. 



Propylene also forms a compound 

 with mercuric sulphate in acid solution 

 which readily decomposes with the for- 

 mation Q^acrolein [lOl] (Deniges,Comp. 



Rend. 126, 1145). The latter oxidises 

 readily to acrylic acid, which can be 

 converted into a-chlorlactic acid, glyceric 

 acid, pyrotartaric or pyroracemic acid, 

 allylene, &c. (see under P, I, M). 



NOTE : All the generators of propylene re- 

 ferred to under glycerol [48 ; B ; C ; D ; E ; 

 F ; G, &c.] can be regarded as sources of allyl- 

 ene as above. 



[P.] Glycerol [48] gives rise to allyl 

 alcohol or iodide (see under ethyl alco- 

 hol [14 ; G] and under isobutyl alcohol 

 [18 ; D]), either of which can be con- 

 verted into allyl chloride (Oppenheim, 

 Ann. 14O, 205 ; Tollens, Ann. 156, 

 154 ; Eltekoff, Journ. Russ. Soc. 14, 

 394). The latter on heating with strong 

 aqueous hydrochloric acid at 100 gives 

 propylene chloride (Reboul, Ann. Chim. 

 [5] 14, 453), which by the action of 

 alcoholic -potash yields a mixture of a- 

 and -chlorpropylene (IbicL, loc. cit. 

 46^^ the latter on further treatment 

 >mh alcoholic potash giving allylene 

 / (Friedel, Ann. 134, 262), which can be 

 converted into mesitylene and toluene 

 as under E and D. 



Or the allyl iodide can be converted 

 into allyl cyanide by the action of 

 potassium cyanide [172] (Glaus, Ann. 

 131, 58 ; Rinne and Tollens, Ann. 159, 

 1 06), and then into a-crotonic acid by 

 heating with potash solution (Will and 

 Korner, Ann. 125, 273). The crotonic 

 acid can be converted into allylene as 

 under G-. 



Or the allyl iodide can be converted 

 into pyrotartaric (methylsuccinic) acid 

 by heating with alcoholic potassium 

 cyanide and decomposition of the product 

 with potash (Glaus, Ann. 191, 37 ; Ber. 

 5, 612 ; Euler, Ber. 28, 2952). The 

 pyrotartaric acid can be converted into 

 citrabrompyrotartaric acid and then into 

 allylene as under N. 



Glycerol on oxidation with nitric acid 

 (Debus, Phil. Mag. [4] 15, 195 ; Ann. 

 106, 79 ; Sokoloff, Rid. 95 ; Mulder, 

 Ber. 9, 1902; Beilstein, Ann. 12O, 

 226), with bromine and water (Barth, 

 Ann. 124, 341) or mercuric oxide in 

 presence of barium hydroxide (Born- 

 stein, Ber. 18, 3357) gives glyceric acid 

 which on dry distillation yields, among 

 other products, pyrotartaric acid (Mol- 



