214 



AROMATIC ALDEHYDES AND KETONES [117 E-J. 



by nitration (Beilstein and Kuhlberg, 

 Ann. 163, 125; Morgan, Ch. News, 

 36, 269 ; Baeyer, Ber. 13, 2258 ; 

 Miiller, Ann. 212, 142 ; Drewsen, 

 Ibid. 151; Fischer and Kiizel, Ann. 

 221, 265), o-nitrophenylpropiolic acid 

 by bromination of o-nitrocinnamic acid 

 and the action of excess of caustic soda 

 on the product (Baeyer, loc. cit.), and 

 o-nitrophenylacetylene by heating o- 

 nitrophenylpropiolic acid with water 

 (Ibid. 2259). o-Nitrophenylacetylene 

 on reduction with zinc dust and am- 

 monia gives o-aminophenylacetylene 

 (Baeyer and Landsberg, Ber. 15, 60 ; 

 Baeyer and Bloem, Ber. 17, 964). The 

 latter, on treatment with sulphuric 

 acid and water, yields o-aminoaceto- 

 phenone (B. and B. Ber. 15, 2154), 

 which can be converted into o-hydroxy- 

 acetophenone, ketocoumaran, and sali- 

 cylic aldehyde as above under D. 



Or from cinnamic acid through 

 phenylpropiolic acid, phenylacetylene, 

 and acetophenone (see under benzoic 

 aldehyde [114; E]), and then as above 

 under D. 



Or from cinnamic acid through 

 coumarone (see under phlorol [64 ; F]), 

 and then as under A above. 



[P.] From benzole acid and aceto- 

 acetic ester [Vol. II]. Benzoic acid on 

 nitration gives (with m- and p-nitro-) 

 some o-nitro-acid (Griess, Ann. 166, 

 129 ; Ber. 10, 1871 ; Ernst, Jahresber. 

 1860, 299; Holleman, Zeit. physik. 

 Ch. 31, 79). o-Nitrobenzoyl chloride 

 and sodio-acetoacetic ester give o- 

 nitrobenzoylacetoacetic ester (Gevekoht, 

 Ann. 221, 323), which on hydrolysis 

 with dilute sulphuric acid yields o-nitro- 

 acetophenone (Ibid. 325). Subsequent 

 steps as above under D. 



Or from benzoic and acetic acids 

 through acetophenone (see under benzoic 

 aldehyde [114; G]), and then as above 

 under D. 



Or from benzoic acid (benzoyl chlor- 

 ide) and zinc metfiyl through aceto- 

 phenone [114 ; C], and then as under D. 



[G.] From salicylic acid [Vol. II] 

 through the ethyl ester of the methyl 

 ether (Cahours, Ann. 92, 315 ; Graebe, 

 Ann. 139, 137), and condensation of the 

 latter with acetic ester [Vol. II] to form 



2-methoxybenzoylacetic ester (Tahara, 

 Ber. 25, 1306). The latter on hydro- 

 lysis with dilute sulphuric acid gives 

 o-methoxyacetophenone, which can be 

 demethylated by heating with hydro- 

 chloric acid at 130 (Ibid. 1309). The 

 o-hydroxyacetophenone can be treated 

 as above under D (see also Besthorn, 

 Banzhaf, and Jaegle, Ber. 27, 3035). 



[H.] Coumarin [Vol. II] on combina- 

 tion with bromine forms a dibromide, 

 which on treatment with alcoholic 

 potash gives o-coumarilic acid (Perkin, 

 Journ. Ch. Soc. 24, 45 ; Fittig and 

 Ebert, Ann. 216, 163). The ethyl 

 ether of the coumarilic acid on heating 

 with dilute hydrochloric acid yields, 

 among other products, o-ethoxyaceto- 

 phenone (Fittig and Claus, Ann. 269, 

 10), which might be de-alkylated and 

 treated as above under G. Or from 

 coumarin through coumarone (see under 

 phlorol [64; D]), and then as above 

 under A. 



[I.] Orthocoumaric acid [Vol. II] on 

 ethylation gives the /3-ethyl ether of 

 the acid (Fittig and Ebert, Ann. 216, 

 146), and this on combination with 

 bromine yields the ethyl ether of di- 

 brom-melilotic acid (Ibid. 158). The 

 latter, by the action of alcoholic potash, 

 gives the ethyl ether of o-coumarilic 

 acid (Fittig and Claus, Ann. 269, 6), 

 which can be treated as above under H. 



[J.] From toluene [54 ; A and D to 

 end] through o-nitrotoluene (see under 

 o-cresol [61 ; A]) and o-nitrobenzoic 

 acid by oxidation of the latter (Wid- 

 mann, Ann. 193, 225 ; Noyes, Ber. 16, 

 53 ; Monnet, Reverdin, and Noelting, 

 Ber. 12,443). Subsequent steps through 

 o-nitrobenzoylacetoacetic ester as above 

 under F. 



Or from o-nitrotoluene through o- 

 nitrobenzaldehyde (see under saligenin 

 [55 ; Cl), which condenses with malonic 

 acid [Vol. II] in presence of aniline to 

 form o-nitrocinnamic acid (Knoevenagel 

 and Baebenroth, Ber. 31, 2609). From 

 the latter through o-nitrophenylpropiolic 

 acid, Sec., as above under E. 



Or from benzene [6 ; I, &c.] through 

 nitrobenzene, aniline, o-nitraniline 

 (Nietzki and Benckiser, Ber. 18, 295 ; 

 Lellmann, Ann. 221, 6; Turner, Ber. 



