112 



AROMATIC ALCOHOLS AND PHENOLS [54 I-K. 



oxide (B. and O., Ber. 10, 264; 18, 

 328). Pyroracemic acid gives pyro- 

 tartaric acid among other products by 

 heating to 100 with hydrochloric acid 

 or to 170 per se (De Clermont, Ber. 

 Q, 72; Bb'ttinger, Ber. Q, 837; 1823; 

 Ann. 188, 308 ; De Jong, Rec. Tr. Ch. 

 20, 8 1 ; 21, 191 : see also Wolff, Ann. 

 317, 22). Pyrotartaric acid can be con- 

 verted into allylene, mesitylene, &c., as 

 above. 



Or (more directly) pyroracemic acid 

 gives uvitic acid, among other products, 

 on boiling with baryta water (Finckh, 

 Ann. 122, 184; Bottinger, Ann. 172, 

 341 j 253; 188, 313; 208, 129; Wolff 

 and Heipp, Ann. 305, 125 ; 152), which 

 acid can be converted into toluene, &c., 

 as under D. 



Or uvitic acid may be synthesised by 

 heating a mixture of pyroracemic acid 

 and acetic aldehyde [92] with baryta 

 water (Doebner, Ber. 23, 2377). 



Acetic and pyroracemic acids are also 

 generators of toluene through phthalide- 

 dicarboxylic acid (see under cymene [6 ; 

 IX]). 



Acetic acid can be converted into 

 acetyl cyanide by the interaction of 

 acetyl chloride and silver cyanide (Hiib- 

 ner, Ann. 120, 334; 124, 315); the 

 cyanide on hydrolysis gives pyroracemic 

 acid (Claisen and Shadwell, Ber. 11, 

 620 ; 1563), which yields uvitic acid, 

 &c., as above. 



Acetoacetic ester by the action of 

 nitrous acid gives isonitrosoacetone 

 (Meyer and Ziiblin, Ber. 11, 695 ; 

 Ceresole, Ber. 15, 1328), which, by the 

 action of acetyl chloride, yields acetyl 

 cyanide (Claisen and Manasse, Ber. 20, 

 2196). The latter can be converted into 

 pyroracemic acid as above. 



Acetoacetic ester by the interaction 

 of the sodium derivative and a-brom- 

 propionic ester (Friedel and Machuca, 

 Ann. 120, 286 ; Comp. Rend. 53, 408 ; 

 Bischoff, Ann. 206, 319 ; Zelinsky, 

 Ber. 20, 2026) gives /3-methylaceto- 

 succinic ester (Conrad, Ann. 188, 226 ; 

 Bischoff, loc. cit. 320) : the latter on 

 treatment with alcoholic potash yields 

 pyrotartaric acid (Conrad, loc. cit. 227). 



Or by the interaction of chloracetic 

 ester and sodio-acetoacetic ester aceto- 



succinic ester is formed (Conrad, loc. cit. 

 21 8; Rach, Ann. 234, 36), which by 

 the action of sodium and metfiyl iodide 

 gives a-methylacetosuccinic ester (Kress- 

 ner, Ann. 192, 135) : the latter on treat- 

 ment with alcoholic potash also yields 

 pyrotartaric acid (Ibid. 138). 



Or the a- and /3-methylacetosuccinic 

 esters on heating with hydrochloric acid 

 give /3-acetyl butyric and ^3-acetylisobu- 

 tyric acids respectively (Bischoff, Ann. 

 206, 319 and 331). Both these acids 

 on oxidation with dilute nitric acid yield 

 pyrotartaric acid (Ibid. 337) with other 

 products. 



Acetoacetic ester also by the action 

 of methyl iodide on its sodium deriva- 

 tive gives methylacetoacetic ester, which 

 by the successive action of bromine and 

 alcoholic potash yields mesaconic acid 

 (Demar^ay, Ann. Chim. [5] 20, 473 ; 

 Gorboff, Journ. Russ. Soc. 19, 605 ; 

 Cloez, Bull. Soc. [2] 3, 598 and 602; 

 Wolf, Ann. 260, 89 ; Ssemenoff, Journ. 

 Russ. Soc. 23, 430 ; 30, 1009 ; Conrad, 

 Ber. 32, 1005). Potassium mesaconate 

 solution gives allylene on electrolysis 

 (Aarland, Journ. pr. Ch. [2] 7, 142). 



Acetoacetic ester by the action of 

 phosphorus pentachloride gives a mix- 

 ture of /3-chlor-a- and /3-crotonic acids 

 (Frolich, Zeit. [2] 5, 270 ; Geuther, 

 ibid. [2], 7, 237 ; Autenrieth, Ann. 259, 

 359; Fittig, Ann. 268, 13). Both 

 these acids by the action of potassium 

 hydroxide give tetrolic (2-butinic) acid 

 (Geuther, loc. cit. 245 ; Friedrich, Ann. 

 219, 319, 342; Kahlbaum, Ber. 12, 

 2338; Fittig and Clutterbuck, Ann. 

 268, 96 : see also Desgrez, Bull. Soc. 

 [3] 11, 391). Tetrolic acid is decom- 

 posed at 210 into carbon dioxide and 

 allylene. 



[J.] Allyl isothiocyanate [166] by the 

 action of zinc dust is converted into 

 allyl cyanide (Schwarz, Ber. 15, 2508), 

 which can be converted into a-crotonic 

 acid, allylene, &c., as under F. Water 

 also in contact with allyl isothiocyanate 

 gives allyl cyanide (Will and Kb'rner, 

 Ann. 125, 272). 



[K.] From normal butyric acid [Vol. 

 II] through the a-bromo-acid (see under 

 n-propyl alcohol [15 ; P]), which gives 

 crotonic acid when the ethyl ester is 



