114 G-115 A.] 



BENZOIC ALDEHYDE 



211 



carbonate and sodium ethylate on the 

 ketone (Claisen, Ber. 2O, 656), or by 

 the action of carbon dioxide on the 

 sodium compound of acetophenone sus- 

 pended in dry ether (Beckmann and 

 Paul, Ann. 266, 17). Benzoylacetic 

 ester can be converted into phenyl-/3- 

 lactic acid, and the latter into benzoic 

 aldehyde as above under C. 



Acetophenone, formic acid [Vol. II], 

 and ethyl alcohol [14] give benzoyl- 

 acetaldehyde by the action of sodium 

 ethylate on a mixture of the ketone and 

 formic ester (Claisen and Fischer, Ber. 

 2O, 2192; 21, 1135). The oxime of 

 this aldehyde gives i 2 -cyanacetophenone 

 by dehydration (Claisen and Stock, Ber. 

 24, 133), and this yields benzoylacet- 

 iminoethyl ether (see above under A), 

 benzoylacetic ester, phenyl-^-lactic acid, 

 and benzoic aldehyde as under C. Or 

 benzoylacetaldoxime by the action of 

 acetyl chloride gives phenylisoxazole, 

 and this yields i 2 -cyanacetophenone by 

 the action of sodium ethylate (Ibid. 



Or acetophenone, oxalic acid [Vol. II], 

 and ethyl alcohol [14] give benzoylpyro- 

 racemic acid by the action of sodium 

 ethylate (Beyer and Claisen, Ber. 2O, 

 2184; Claisen and Bromme, Ber. 21, 

 1132), the oxime of which, treated with 

 acetyl chloride, gives phenylisoxazole- 

 carboxylic acid (Salvatori, Gazz. 21, II, 

 286). The latter yields i 2 -cyanaceto- 

 phenone on heating (Ibid. 287). 



[H.] From phenol [6O] through tri- 

 phenyl phosphate by the action of phos- 

 phorus pentachloride or oxychloride 

 (Williamson and Scrugham, Journ. Ch. 

 Soc. 7, 240; Heim, Ber. 16, 1/65), 

 benzonitrile by distilling the phosphate 

 vi\k\\ potassium cj/anide[l72] (Scrugham, 

 Ann. 92, 318; Heirn, loc. cit. 1771), 

 and then (with acetonitrile) through 

 iminobenzoylmethyl cyanide, &c., as 

 above under A and C. 



[I.] Hippuric acid [Vol. II] gives 

 benzonitrile on heating per se or with 

 zinc chloride (Limpricht and Uslar, Ann. 

 88, 133; Gossmann, Ann. 10O, 74). 

 Subsequent steps as above. 



[J.] From naphthalene [12] (see under 

 hydrojuglone [00]), through phthalic 

 acid (benzyl alcohol [54; R]), and 



phthalimide by the action of ammonia 

 on phthalic anhydride (Laurent, Ann. 

 41, no; Lansberg, Ann. 215, 181). 

 The imide gives benzonitrile on dis- 

 tillation with lime (Laurent, Jahresber. 

 1868, 549; Reese, Ann. 242, 5). Sub- 

 sequent steps as above. 



[K.] From cymene [6] through cumic 

 aldehyde [116] and cumic acid by oxi- 

 dation ( Gerhard t and Cahours, Ann. 

 38, 74; Beilstein and Kupfer, Ann. 

 17O, 302 ; E. Meyer, Ann. 219, 244), 

 isopropylbenzene (cumene) by distilling 

 the acid with lime or baryta (G. and C. 

 loc. cit. 88 ; Ann. China. [3] 1, 87 ; 372 ; 

 14, 107), acetophenone, &c., as above 

 under A, G-, and C. 



[L.] Benzyl alcohol [54] gives ben- 

 zoic aldehyde on oxidation with dilute 

 nitric acid, &c. Or by pyrogenic con- 

 tact decomposition by heated copper 

 (Ipatieff, Ber. 35, 1055). 



[M.] From racemic or tartaric acid 

 [Vol. II] and n-propyl alcohol [15] 

 through pyroracemic acid, ethyliso- 

 phthalic acid, and ethylbenzene (see 

 under phlorol [64; J]), and then as 

 above under A. 



Or from pyroracemic acid and isolu- 

 tyric aldehyde [94] through isopropyl- 

 benzene (see under cymene [6; A, note]), 

 and then as above under A. 



115. Hydrociniiamic Aldehyde; 

 Plieiiylpropionic Aldehyde ; 

 Fhenepropylal. 



C 6 H 5 .CH 2 .CH 2 .CHO 



NATURAL SOURCE. 



May possibly occur in Ceylon oil of 

 cinnamon (SchimmePs Ber. April, 1902; 

 Walbaum and Hiithig, Journ. pr. Ch. 

 [2] 66, 52). 



SYNTHETICAL PROCESSES. 



[A.] From n-propyl alcohol [15] and 

 benzene [6; I, &c.] through propylben- 

 zene by the condensation of propy] 

 bromide and brombenzene by the action 

 of sodium (Fittig, Schaffer, and Konig, 

 Ann. 149, 324), or of aluminium chloride 

 (Heise, Ber. 24, 768). Propy Ibenzene 



