114 



AROMATIC ALCOHOLS AND PHENOLS [54 M-B. 



Oxalic and propionic acids [Vol. II] and alcohol 

 [14] through methyloxalacetic ester by the 

 action of sodium ethoxide followed by that of 

 ethyl propionate on oxalic diethyl ester (Ar- 

 nold, Ann. 246, 329). Methyloxalacetic ester 

 gives (3 - methylmalic (2-methyl-3-butanoldi- 

 carboxylic) acid on reduction with sodium amal- 

 gam (Wislicenus, Ber. 25, 199), and this acid 

 gives citraconic anhydride and mesaconic acid 

 on distillation. 



[N.] Tartar ic acid [Vol. II] through 

 pyrotartaric (methylsuccinic) acid (see 

 under normal propyl alcohol [15 ; V]), 

 citrabrompyrotartaric acid by the action 

 of bromine and phosphorus (Auwers 

 and Imhauser, Ber. 24, 22,36), and then 

 through allylene, &c., as under M. 



Racemic acid also gives pyrotartaric 

 acid on distillation (references as under 

 normal propyl alcohol [15 ; V]). 



Both tartaric and racemic acids give 

 pyroracemic acid among the products of 

 their distillation (Berzelius, Pogg. Ann. 

 36, I ; Ann. 13, 6 1 ; Volckel, Ann. 

 89, 65; Wislicenus, Ann. 126, 225). 

 Tartaric acid gives pyroracemic acid by 

 heating to 180 with hydrochloric acid 

 (Geuther and Riemann, Zeit. [a] 5, 

 318), to 40 with strong sulphuric acid 

 (Bouchardat, Comp. Rend. 89, 99), or 

 by dry distillation per se, or mixed with 

 sand, or with acid potassium sulphate 

 at 220 (Clewing, Journ. pr. Ch. [2] 17, 

 243 ; Erlenmeyer, Ber. 14, 320 ; Dobner, 

 Ann. 242, 269; Seissl, Ann. 249, 

 297 ; Erdmann, Zeit. f. Naturwissen- 

 schaften, 71, 385). Pyroracemic acid 

 is produced in aqueous solutions of tar- 

 taric acid by photochemical action 

 (Otto, Ber. 27, 838 ; 1264). Pyrorace- 

 mic acid can be converted into uvitic 

 acid, &c., as under I. (For conversion 

 of acetic and pyroracemic acids into 

 toluene via phthalidedicarboxylic acid 

 see under cymene [6 ; IX].) 



[O.] Propionic acid [Vol. II] on bro- 

 mination gives aa-dibrompropionic acid 

 (Friedel and Machuca, Comp. Rend. 

 54, 22O; Philip pi and Tollens, Ann. 

 171, 315; Epstein, Comp. Rend. 124, 

 688), which on long heating with fum- 

 ing hydrobromio acid solution is con- 

 verted into the a/3-acid (P. and T. loc. 

 cit. 337). The latter on heating with 

 water and silver oxide gives gly eerie 

 acid (Beckurts and Otto, Ber. 18, 238), 



which furnishes pyrotartaric acid, &c., 

 as under P, M, and N. 



Or the aa-dibrompropionic acid on 

 heating with silver carbonate and water 

 yields pyroracemic acid (Ibid. 235), 

 which gives uvitic acid, &c., as under 

 I and D. 



Or the propionic acid can be con- 

 verted into propionamide and propioni- 

 trile (Dumas, Malaguti, and Leblanc, 

 Ann. 64, 334), and then into aa-dichlor- 

 propionic acid, pyroracemic acid, &c., as 

 before. 



Or through propionyl chloride and 

 /3-chlorpropionic acid, which gives acrylic 

 acid on heating with barium hydroxide 

 solution (Michael and Garner, Ber. 34, 

 4047). From acrylic through a-chlor- 

 lactic to gly eerie and pyrotartaric or 

 pyroracemic acid as before. 



[P.] Lactic acid [Vol. II] gives 

 pyroracemic acid by oxidation of the 

 calcium salt with potassium perman- 

 ganate (Beilstein and Wiegand, Ber. 

 17, 840). Subsequent steps as above. 



Or from lactic acid through a-chlor- 

 propionic acid (Wurtz, Ann. Chim. [3] 

 49, 58 ; Briihl, Ber. 9, 35), which on 

 heating with barium hydroxide solution 

 gives acrylic acid (Michael and Garner, 

 Ber. 34, 4050). From the latter through 

 a-chlorlactic to glyceric and pyrotartaric 

 or pyroracemic acid as before. 



[Q.] Isovaleric acid [Vol. II] gives 

 mesitylenic acid among other products 

 when the dry sodium salt mixed with 

 sodium ethoxide is heated in the pre- 

 sence of carbon monoxide at 160 (Loos, 

 Ann. 202, 321). Mesitylenic acid gives 

 uvitic acid on oxidation (Fittig and v. 

 Furtenbach, Zeit. [2] 4, I ; Ann. 147, 

 295), and the latter yields toluene as 

 under D. 



NOTE : Allylene is among the products formed 

 when the vapours of acetone [106], ethyl [14], 

 propyl [15], isobutyl [18], and amyl [22] alcohols 

 are passed over hot magnesium, and the product 

 decomposed by water (Keiser and Breed, Ch. 

 News, 71, 118 ; Keiser, Am. Ch. Journ. 18, 328). 



Generators of Toluene through Toluic 

 Acid. 



[R.] Naphthalene [12] and deriva- 

 tives by various processes of oxidation 

 give phthalic acid (Laurent, Ann. 19, 

 38; Ann. Chim. [2] 61, 113 ; Marignac, 



