134 



AROMATIC ALCOHOLS AND PHENOLS 



[64 C-J. 



chloride (in acetic acid solution) con- 

 denses to coumarone (Stoermer, Ber. 

 30, 1703), and this can be reduced to 

 phlorol as below under D. 



[D.] From conmarin [Vol. II] through 

 the chloride or bromide (Perkin, Zeit. 

 [2] 1, 178; Journ. Ch. Soc. 17, 368; 

 24, 37; Ann. 157, 116; Fittig and 

 Ebert, Ann. 216, 163), u-chlor- or a- 

 bromcoumarin (Perkin, loc. cit. ; also 

 Journ. Ch. Soc. 23, 368), o-couma- 

 rilic acid by the action of alcoholic 

 potash (Ibid. Journ. Ch. Soc. 24, 

 45 ; Fittig and Ebert, loc. cit.), 

 coumarone by heating coumarilic acid 

 with lime (Fittig and Ebert, loc. cit. 

 1 68 and 226, 347), and reduction of 

 coumarone in hot alcoholic solution with 

 sodium, hydrocoumarone being simul- 

 taneously formed (Alexander, Ber. 25, 

 2410). 



The conversion of hydrocoumarone 

 into o-ethylphenol can also be effected 

 by boiling with strong hydriodic acid 

 solution (Baeyer and Seuffert, Ber. 34, 

 52). Coumarone also gives o-ethyl- 

 phenol among the products of its de- 

 composition by alcoholic alkali (Stoermer 

 and Kahlert, Ber. 35, 1630). 



[E.] From salicylic aldehyde [117] 

 and acetic acid [Vol. II] through o- 

 aldehydophenoxyacetic acid (aldehydo- 

 phenylglycollic acid) by the action of 

 chloracetic acid on the sodium compound 

 of the aldehyde (Rossing, Ber. 17, 2990), 

 coumarone by heating the aldehyde acid 

 with acetic anhydride and sodium ace- 

 tate (Ibid. 3000), and then as under D. 

 [F.] Cinnamic acid [Vol. II] when 

 nitrated gives a mixture of o- and p- 

 nitro-acids (Beilstein and Kuhlberg, 

 Ann. 163, 126; Morgan, Ch. News, 

 36, 269 ; Jahresber. 1877, 788; Miiller, 

 Ann. 212, 124; Drewsen, Ann. 212, 

 151 ; Fischer and Kuzel, Ann. 221, 

 265). The former, by the action of hypo- 

 chlorous acid on the sodium salt, yields 

 (with o - nitrophenylchlorlactic acid) 

 i 2 -chlor-2-nitrostyrene = o-nitrophenyl- 

 a>-chlorethylene (Lipp, Ber. 17, 1070), 

 which, by reduction and the diazo- 

 method, gives i~-chlorvinylphenol = o- 

 hydroxy-oo-chlorstyrene (Komppa, Ber. 

 26, 2970). The latter when heated 

 with strong potash solution yields 



coumarone (Ibid. 2971), which can be 

 converted into phlorol as under D. 



[G.] Benzole aldehyde [114] on nitra- 

 tion gives (with much m-nitro-) a small 

 quantity of o-nitro-aldehyde (Rudolph, 

 Ber. 13, 310), which, on heating with 

 acetic anhydride and sodium acetate, 

 yields o-nitrocinnamic acid (Gabriel and 

 Meyer, Ber. 14, 830). The latter can 

 be converted into coumarone and phlorol 

 as under P. 



NOTE : For o-nitrobenzaldehyde generators 

 see also under indigo [Vol. II]. 



[H.] From pk&nylacetic acid [Vol. II] 

 through the 2 : 4-dinitro-acid by nitra- 

 tion (Radziszewski, Ber. 2, 210; Gabriel 

 and Meyer, Ber. 14, 823), 2-nitro-4- 

 amino-acid by reduction, the diazo- 

 chloride by the action of nitrous acid 

 in presence of hydrochloric acid, o-nitro- 

 benzaldoxime by heating the diazo- 

 chloride with alcohol, o-nitrobenzalde- 

 hyde by oxidising the aldoxime with 

 chromic acid (Gabriel and Meyer, loc. 

 cit. and 15, 3057 ; Gabriel, Ibid. 16, 

 520), and then as under G. 



[I.] Acetoacetic ester [Vol. II] and 

 benzene can give rise to phlorol by the 

 following steps : 



Benzene is brominated, the mono- 

 brombenzene converted by cold nitration 

 into brotn-2 : 4-dinitrobenzene (Kekule, 

 Ann. 137, 167 ; Spiegelberg, Ann. 197, 

 257 : see also Walker and Zincke, Ber. 

 5, 117), the latter combined with 

 sodio-acetoacetic ester so as to form 2 : 

 4-dinitrophenylacetoacetic ester (Heck- 

 mann, Ann. 220, 131 : a bis-dinitro- 

 phenyl derivative is formed simul- 

 taneously). The dinitrophenyl ester on 

 heating in alcohol with 10 per cent, 

 sulphuric acid is converted into 2 : 4- 

 dinitrophenylacetic acid (Ibid. 134), 

 which can be treated as above. 



[J.] Hacemic or tartar ic acid [Vol. II] 

 and n-prop'/l alcohol [15] are generators 

 of ethylbenzene, and therefore of 

 phlorol, by the following steps : 



Pyroracemic acid is obtained from the 

 above acids by dry distillation or other 

 method (see under benzyl alcohol [54 ; 

 N]), and this, when mixed withpropiouic 

 aldehyde and barium hydroxide solution, 

 condenses to 1:3: 5-ethylisophthalic 



