122 



AROMATIC ALCOHOLS AND PHENOLS [eo H-J. 



Ber. Q, 146 ; Friedlander and Hen- 

 riques, Ber. 14, 2802 ; Ehrlich, Ber. 

 15, 2010), m-nitrobenzylidene chloride 

 (i 1 : 1 1 -dichlor-3-nitro toluene) by the 

 action of phosphorus pentachloride 

 (Widman, Ber. 13, 676), m-toluidine 

 by reduction (Vienne and Steiner, Bull. 

 Soc. [2] 35, 428 ; Widman, loc. 

 cit. 677; Bull. Soc. [2] 36, 216; 

 Ehrlich, Ber. 15, 2011; Harz, Ber. 

 18, 3398), m-chlortoluene by the diazo- 

 reaction (Wroblewski, Ann. 168, 199), 

 m-chlorbenzoic acid by oxidation (Ibid. 

 200), m-hydroxybenzoic acid, &c., as 

 under E. 



Or the m-nitrobenzoic aldehyde might 

 be directly oxidised to m-nitrobenzoic 

 acid, reduced to m-aminobenzoic acid, 

 and then converted into m-hydroxy- 

 benzoic acid and phenol as under E. 

 The aldehyde can also be converted 

 (partially) into m-chlorbenzaldehyde 

 by the action of iodine and antimony 

 pentachloride (Gnehm and Banziger, 

 Ber. 29, 875), and then oxidised to 

 m-chlorbenzoic acid and treated as 

 under E. 



[I.] Metacresol [62] is said to give 

 m-hydroxybenzoic acid on fusion with 

 potash (Barth, Ann. 154, 361 ; Monats. 

 3, 802), and this can be converted into 

 phenol as under E. 



[J.] Naphthalene [12] when nitrated 

 gives a-nitronaphthalene (Laurent, Ann. 

 Chim. [2] 59, 378 ; Piria, Ann. 78, 32 ; 

 Beilstein and Kuhlberg, Ann. 169, 83), 

 which on oxidation yields 3-nitrophthalic 

 acid (Guareschi, Ber. 10, 294 ; Beil- 

 stein and Kurbatoff, Ann. 202, 217). 

 The latter on reduction with tin and 

 hydrochloric acid gives m-aminobenzoic 

 acid (Faust, Ann. 160, 61 ; Miller, 

 Ann. 208, 245), which can be con- 

 verted into m-hydroxybenzoic acid and 

 phenol as under E. 



Or the reduction can be regulated so 

 as to give 3-aminophthalic acid (Miller, 

 loc. cit.), from which, by the diazo- 

 method, 3-hydroxyphthalic acid can be 

 obtained (Bernthsen and Semper, Ber. 

 18, 167 ; 2O, 937), and this gives phenol 

 on heating. 



Or from naphthalene through phthal- 

 ic acid, phthalide, &c., to o-toluic acid 

 (see under benzyl alcohol [54; B,]), or 



through 1:3: 8-naphthylaminedisul- 

 phonic acid, &c., to o-toluic acid (Ibid.]. 

 The latter on sulphonation gives 6- 

 sulpho-o-toluic acid (Jacobsen and 

 Wierss, Ber. 16, 1959), from which, by 

 potash fusion, 6-hydroxy-o-toluic acid 

 can be obtained (Ibid. 1963). 



Or o-toluic acid can be converted into 

 the 6-hydroxy-acid through the 6- 

 nitro- and 6-amino-acid and diazo- 

 method (Ibid. 17, 163). The 6-hydroxy- 

 o-toluic acid is converted into the 

 methoxy-o-toluic acid by methylation, 

 and the latter on oxidation with alka- 

 line permanganate gives 3-methoxy- 

 phthalic (3-methoxy- 1 : 2-dicarboxylic) 

 acid, which yields 3-hydroxyphthalic 

 acid on fusion with alkali (Jacobsen, 

 Ber. 16, 1965). The latter acid gives 

 phenol when heated. 



Phthalic acid also may be nitrated, 

 and the 4-nitro- (separated from the 

 3-nitro-) acid (Miller, Ann. 208, 224) 

 converted into ester and reduced to 

 4-aminophthalic ester, which by the 

 diazo-method and hydrolysis gives 4- 

 hydroxyphthalic acid (Baeyer, Ber. 10, 

 1079; Miller, Ber. 11, 1191; Ann. 

 208, 237). The latter on heating with 

 hydrochloric acid yields m-hydroxyben- 

 zoic acid, from which phenol can be 

 obtained as under E. 



Or phthalic acid may be sulphonated 

 by fuming sulphuric acid (Loew, Ann. 

 143, 257; Ree, Ann. 233, 219), the 

 4-sulphophthalic acid converted into 

 4-hydroxyphthalic acid by fusion with 

 alkali (Graebe, Ber. 18, 1130 ; Ree, loc. 

 cit.}, and the latter converted into m- 

 hydroxybenzoic acid and phenol as 

 above. 



Naphthalene may also be converted 

 into a-sulphonic acid and a-naphthol 

 (Eller, Ann. 152, 275), the latter into 

 acetate, and the acetate oxidised by 

 chromic acid into 3-hydroxyphthalic 

 acid (Miller, Ann. 208, 247), from 

 which phenol can be obtained as above. 

 [The acid thus obtained by Miller is 

 said to have been 2-hydroxyisophthalic 

 acid, but from its mode of formation 

 must be 3-hydroxyphthalic acid (Beil- 

 stein, II, 1936 and errata, 2209).] 



Or naphthalene-ct-sulphonic acid may 

 be converted into the sulphonamide, 



