122 A-124 A.] 



PIPERONAL 



223 



chloroform [l ; D] in presence of aqueous 

 caustic soda (Tiemann and Reimer, Ber. 

 9, 1 269 ; Tiemann and Koppe, Ber. 14, 

 2015). The aldehyde gives piperonal 

 on treatment with methylene iodide (see 

 under ethyl alcohol [14 ; I ; M]) and 

 potassium hydroxide in methyl alcohol 

 (Wegscheider, Monats. 14, 388). 



[B.] Piperic acid [Vol. II] gives 

 piperonal on oxidation with potassium 

 permanganate in neutral or alkaline 

 solution (Fittig and Mielck, Ann. 152, 

 35 ; Doebner, Ber. 23, 2375). 



123. Cinnamic Aldehyde ; 

 Phenepropenylal ; /3-Fhenylacrolein. 



CH : CH . CHO 



SYNTHETICAL PROCESSES. 



NATURAL SOURCES. 



In oil of cinnamon from Cinnamomitm 

 zeylanicnm, Ceylon (Dumas and Peligot, 

 Ann. Chim. 57, 305 ; Ann. 14, 50), and 

 in oil of cassia from C. cassia (Ibid. ; 

 Ann. 12, 24; 13, 76; 14, 50). The oil 

 is obtained from the bark, waste twigs, 

 and root of C. zeylanicum. Oil of 

 cinnamon leaf contains eugenol and 

 but little cinnamic aldehyde (Weber, 

 Arch. Pharm. 230, 728). 



Oil of cassia (Chinese) is prepared 

 from leaves, flower and leaf stalks, buds 

 and twigs of C. cassia, the oils from 

 these parts of the shrub all containing 

 the aldehyde as well as the oil from the 

 bark (Schimmel's Ber. Oct. 1892). 



Occurs also in oil of Cinnamomum 

 loureirii from Japan (Shimoyama; 

 Gildemeister and Hoffmann, p. 509), 

 and in rassamala resin from the Javan 

 Allingia excel sa (Tschirch and Van 

 Itallie, Arch. Pharm. 239, 541)- 



Cinnamic aldehyde is said to be 

 among the products of the pancreatic 

 fermentation of fibrin (Ossikowszky, 

 Bsr. 13, 326). 



[A.] From benzoic aldehyde [114] and 

 acetic aldehyde [92] by saturating a 

 mixture of the two aldehydes with hy- 

 drogen chloride, and then heating 

 (Chiozza, Ann. 97, 350). Or by allow- 

 ing the mixed aldehydes to remain in 

 contact with dilute caustic soda solution 

 (Peine, Ber. 17, 2117). The condensa- 

 tion of the aldehydes is best effected 

 by alcoholic sodium hydroxide at 10 

 (Bohringer & Sohne, Eng. Pat. 10003 

 of 1896 ; Journ. Soc. Ch. Ind. 16, 



463). 



[B.] From cinnamic acid [Vol. II] 

 by distilling the calcium salt with cal- 

 cium, formate [Vol. II] (Piria, Ann. 100, 



124. Orthocouniaric Aldehyde 



Methyl Ether; Orthomethoxy- 



cinnamic Aldehyde. 



CH:CH.CHO 



OCH, 



NATURAL SOURCE. 



In oil of cassia, from Cinnamomum 

 cassia (Bertram and Kiirsten, Journ. 

 pr. Ch. [2] 51, 316). 



SYNTHETICAL PROCESS. 



[A.] From salicylic [117] and acetic 

 aldehydes [92] and methyl alcohol [13]. 

 Salicylic aldehyde is converted into its 

 methyl ether by methylating the sodium 

 salt with methyl iodide (Perkin, Trans. 

 Ch. Soc. 55, 550 ; Voswinckel, Ber. 15, 

 2024). o-Methoxybenzoic aldehyde and 

 acetic aldehyde condense when allowed 

 to stand in contact with dilute caustic 

 soda solution to form o-coumaric alde- 

 hyde methyl ether (Bertram and Kiir- 

 sten, Journ. pr. Ch. [2] 51, 316). 



