144 



AROMATIC ALCOHOLS AND PHENOLS 



[70 B-P. 



1088; Brunner, Jahresber. 1819, 759; 

 Fahlberg, Am. Ch. Journ. 2, 188), and 

 the latter converted by potasb fusion 

 (below 25o)into/3-resoi*cylic acid (Blom- 

 strand, loc. cit. ; Fahlberg, loc. cit. 1 96), 

 from wbich resorcinol can be obtained 

 as above. 



[C.] From phenol [60] through p- 

 bromphenol (Hiibner and Brenken, Ber. 

 6, 170 ; Gordon, Proc. Ch. Soc. 7, 64 ; 

 Meldola and F. H. Streatfeild, Trans. 

 Ch. Soc. 73, 681), and fusion with 

 potash (Fittig- and Mager, Ber. 7, 1177; 

 8, 362); the resorcinol in this case being 

 formed by isomeric transformation. 



Or phenol may be converted into o- 

 and p-nitrophenol by nitration, the 

 latter reduced to p-aminophenol, and 

 the NH 2 -group replaced by iodine or 

 chlorine by the diazo-method (Noelting 

 and Strieker, Ber. 20, 3018; Schmitt, 

 Ber. 1, 67 : for references to direct 

 iodising of phenol see under catechol 

 [69 ; A] ; for direct chlorination of 

 phenol see Petersen and Bahr-Praderi, 

 Ann. 157, 1 23 ; also Dubois, Zeit. [2] 2, 

 705; 3, 205). Both p-chlor- and p- 

 iodophenol give resorcinol (by isomeric 

 transformation) when fused with potash, 

 the latter above 165 (Faust, Ber. Q, 

 1022; Noelting and Wrzesinsky, Ber. 

 8, 820). 



Resorcinol is also among the products 

 of fusion of phenol with caustic soda 

 (Barth and Schreder, Ber. 12, 420). 

 The phenolsulphonic acids (see under 

 catechol [69 ; A]) also (by isomeric 

 transformation) give resorcinol when 

 fused with potash (Kekule, Zeit. [2] 3, 

 301). 



[D.] Benzoic acid [Vol. II] when sul- 

 phonated with fuming sulphuric acid in 

 the presence of phosphorus pentoxide 

 gives 3 : 5-disulphobenzoic acid (Barth 

 and Senhofer, Ann. 159, 217), from 

 which by potash fusion 3 : 5-dihydroxy- 

 benzoic (3 : 5-phenediolcarboxylic or a- 

 resorcylic) acid is obtained (Ibid. 222). 

 This acid, on heating with sodium 

 hydroxide above 350, yields resorcinol 

 (Barth and Schreder, Ber. 12, 1258). 



Or benzoic acid may be converted 

 directly or indirectly into m-bromben- 

 zoicacid (Peligot, Ann. 28, 246; Griess, 

 Ann. 117, 25 ; Reinecke, Zeit. [2] 1, 



116; 2, 367; 5, 109; Hiibner, Ohly, 

 and Philipp, Ann. 143, 233 ; Hiibner 

 and Petermann, Ann. 149, 131 ; An- 

 gerstein, Ann. 158, 2 and 5 ; Friedburg, 

 Ibid. 26; Hiibner, Ann. 222, 100), 

 the latter sulphonated by sulphuric an- 

 hydride (Hiibner and Upmann, Zeit. 

 [2] 6, 29,5), the 3-brom-5-sulphobenzoic 

 acid thus formed converted into a-resor- 

 cylic acid by potash fusion (Bb'ttinger, 

 Ber. 8, 374), and then into resorcinol as 

 above. 



[E.] UmbeHiferone [Vol. II] on fusion 

 with potash gives /3-resorcylic acid 

 (Tiemann and Reimer, Ber. 12, 997 ; 

 Tiemann and Parrisius, Ber. 13, 2358), 

 and finally resorcinol (Hlasiwetz and 

 Grabowski, Ann. 139, 99). 



[P.] Ethyl alcohol [14], fftycerol [48], 

 and acetic acid [Vol. II] furnish the 

 resorcinol complex by the following pro- 

 cesses : 



Acetic acid and alcohol give acetic 

 ester, and the latter acetoacetic ester. 

 Glycerol on oxidation with nitric acid 

 or other oxidising agents gives glyceric 

 acid (Debus, Phil. Mag. [4] 15, 1 95 ; Ann. 

 1O6, 79 ; 1O9, 227 ; Sokoloff, Ann. 106, 

 95 ; De la Rue and Miiller, Ann. 109, 

 122; Beilstein, Ann. 12O, 228 ; Barth, 

 Ann. 124, 341 ; Moldenhauer, Ann. 

 131,324; Mulder, Ber. 9 1902; Born- 

 stein, Ber. 18, 3357 ; Lewkowitsch, 

 Proc. Ch. Soc. 5, 14 ; Wohlk, Journ. 

 pr. Ch. [2] 61, 200 ; Zinno, Monit. Sci. 

 16, 493 : see a ^ so un der benzyl alcohol 

 [54 ; F]). Glyceric acid by the action 

 of phosphorus iodide yields /3-iodopro- 

 pionic acid (Beilstein, Ann. 120, 226 ; 

 122, 366 ; Erlenmeyer, Ann. 191, 284; 

 Rosenthal, Ann. 233, 16; Meyer, Ber. 

 19, 3294; 21, 24). The ester of /3- 

 iodopropionic acid condenses with sodio- 

 acetoacetic ester to f^ ; - m acetoglutaric 

 diethyl ester (Wislicer s and Limpach, 

 Ann. 192, 128), which on heating with 

 hydrochloric acid gives y-acetobutyric 

 (5-hexanonic) acid (Fittig and Wolff, 

 Ann. 216, 129; Fittig and Christ, 

 Ann. 268, -113; "W. H. Perkin, junr., 

 Trans. Ch. Soc. 69, 1510). y-Aceto- 

 butyric ester condenses under the in- 

 fluence of sodium ethoxide to diketo- 

 hexamethylene or dihydroresorcinol, 

 from which resorcinol can be obtained 



