130 E 131 C.] ORTHOHYDROXYACETOPHENONE 



229 



coumarilic acid as under salicylic alde- 

 hyde [117; I]. 



[P.] From styrene [?] through phenyl- 

 acetylene and acetophenone (see under 

 benzoic aldehyde [114; B]), and then 

 o-nitroacetophenone, &c., as under A 

 above. 



[G.] From cymene [6] through cumic 

 aldehyde [116] and acid, isopropylben- 

 zene, acetophenone [114 ; K], and then 

 as above under A. 



[H.] Benzene [6 ; I, &c.] becomes a 

 generator of acetophenone, and there- 

 fore of the o-hydroxy-ketone, through 

 ethylbenzene and normal or isopropyl- 

 benzene, or by interaction with acetyl 

 chloride in presence of aluminium 

 chloride [114; A]. Also through acet- 

 anilide and o-aminoacetophenone (see 

 under salicylic aldehyde [117; J]). 



131. Ficeol; Parahyclroxyaceto- 

 phenone ; Para- Acetylplieiiol. 



CO . CH, 



OH 



NATURAL SOURCE. 



Occurs in the form of a glucoside, 

 picein, in the needles of Pinus picea 

 (Tanret, Comp. Rend. 119, 80 ; Bull. 

 Soc. [3] 11, 944). The hydrolysis of 

 picein is capable of being effected by 

 certain enzymes. 



SYNTHETICAL PROCESSES. 



[A.] From phenol [60], methyl alcohol 

 [13], and acetic acid [Vol. II]. Phenol 

 is converted into anisole (see under 

 anisic aldehyde [120 ; B]), and the 

 latter into p-acetyl anisole by adding 

 acetyl chloride to the solution of anisole 

 in carbon disulphide in presence of 

 aluminium chloride (Gattermann, Ehr- 

 hardt, and Maisch, Ber. 23, 1202; 

 Holleman, Rec. Tr. Ch. 10, 215). p- 

 Acetylanisole is demethylated by the 

 action of hydrogen bromide, giving p- 



hydroxyacetophenone (Charon and Za- 

 manos, Comp. Rend. 133, 742). 



NOTE : Phenol and acetyl chloride condenbe 

 also in carbon disulphide solution under the 

 influence of dry ferric chloride with the forma- 

 tion of p-hydroxyacetophenone (Nencki and 

 Stoeber, Ber. 30, 1769 : see also Michael and 

 Palmer, Am. Ch. Journ. 7, 277). 



[B.] Anethole [68] on oxidation with 

 iodine and mercuric oxide gives p- 

 methoxy hydratropic aldehyde (Bou- 

 gault, Comp. Rend. 130, 1766; 131, 

 44; Bull. Soc. [3] 25, 446; Ann. 

 Chim. [7] 25, 514), and this, on oxida- 

 tion with alkaline silver oxide, yields the 

 corresponding acid (Ibid. Comp. Rend. 

 130, 1767; 181, 44). The latter, on 

 further oxidation by chromic acid mix- 

 ture, gives p-methoxyacetophenone(/foV7. 

 Comp. Rend. 132, 782), which can be 

 demethylated as under A. 



NOTE: The following synthetical products 

 are generators of p-methoxyacetophenone via 

 p-methoxyhydratropic acid : 



Toluene through benzyl chloride and cyanide, 

 from which, by the action of methyl iodide and 

 sodium hydroxide, the nitrile of hydratropic 

 acid is obtained (Meyer, Ann. 250, 123 ; 

 Oliveri, Gazz. 18, 574). The acid obtained by 

 hydrolysis gives, on nitration, a mixture of 

 o- and p-nitrohydratropic acid and the latter, by 

 reduction, p-aminohydratropic acid (Trinius, 

 Ann. 227 r 262 ; 267). By the diazo-method 

 the amino-acid yields p-hydroxy hydratropic 

 acid (Ibid- 268), and this, by methylation, the 

 correspon ding p-methoxy-deri vative (Bougaul t, 

 Comp. Rend. .131, 270), 



Acetophenone and hydrogen cyanide yield a cyan- 

 hydrin which, on heating with strong hydriodic 

 acid and red phosphorus, gives hydratropic 

 acid (Janssen, Ann. 250, 136). Subsequent 

 steps as above. 



The esters of pJienylacetic and oxalic acids con- 

 dense under the influence of sodium ethoxide 

 to form the diethyl ester of phenyloxalacetic 

 acid (Wislicenus, Ber. 27, 1092), and this on 

 distillation in vacuo gives phenylmalonic ester 

 (Ibid. 1093). The latter, with methyl iodide 

 and sodium ethoxide, yields phenylmethyl- 

 malonic diethyl ester (Wislicenus and Gold- 

 stein, Ber. 28, 815), the acid of which gives 

 hydratropic acid on fusion (Ibid. 816). 



[C.] Anisic aldehyde [120] on heating 

 with acetic anhydride and sodium 

 acetate gives p-methoxycinnamic acid 

 (Perkin, Jahresber. 1877, 792 ; Journ. 

 Ch. Soc. 31, 408), which combines with 

 bromine to form p-methoxydibrom- 

 dihydrocinnamic acid = the methyl ether 

 of i 1 : i 2 -dibrom-p-hydrocoumaric acid 

 (Eigel, Ber. 20, 2536). The ethyl 



