168 



AROMATIC ALCOHOLS AND PHENOLS [90 A-G. 



109102 of Bayer & Co. ; Germ. Pats. 73381 and 

 73607 of Cassella & Co. See also Dressel and 

 Kothe, Ber. 27, 2139. 



The conversion of naphthalene into 

 the a-quinone, and thence (as above) 

 into juglone, can also be effected through 

 a-naphthylamine, a-acetnaphthalide, I : 

 4-nitroacetnaphthalide, i : 4-nitronaph- 

 thylamine, I : 4-naphthylenediamine, 

 and oxidation of the latter by chromic 

 acid mixture (Liebermann, Ann. 183, 

 2,42, : all azo-derivatives of a-naphthyla- 

 mine give the I : 4-diamine on reduc- 

 tion ; Perkin, Ann. 137, 359 ; Griess, 

 Ber. 15, 2183). 



i : 4-Nitronaphthylamine is also ob- 

 tained by the action of hydroxylamine 

 on a-nitronaphthalene in the presence 

 of sodium ethoxide (Angeli and Angelico, 

 Atti Real. Accad. [5] 8, II, 28; Ch. 

 Centr. 1899, 2, 371). 



Or a-acetnaphthalide can be converted 

 into i : 4-nitronaphthol by boiling the 

 I : 4-nitro-derivative with potash solu- 

 tion (Andreoni and Biedermann, Ber. Q, 

 342, ; Liebermann and Dittler, Ber. 7, 

 240; Hiibner and Ebell, Ber. 8, 562; 

 Ann. 208, 324). The nitronaphthol on 

 reduction gives i : 4-aminonaphthol, and 

 this also oxidises to a-naphthaquinone 

 (Liebermann, Ann. 183, 242 ; Ber. 14, 

 1796 ; Zincke, Ann. 286, 70). 



a-Naphthylamine can also be directly 

 oxidised to the a-quinone by chromic 

 acid mixture (Monnet, Reverdin, and 

 Noelting, Ber. 12, 2306). 



[B.] From benzoic aldehyde [114] and 

 succinic acid [Vol. II] by heating the 

 aldehyde with succinic anhydride and 

 sodium succinate so as to form phenyl- 

 isocrotonic (/3-benzalpropionic = phene- 

 I 1 -butenylic) acid (Perkin, Journ. Ch. 

 Soc. 31, 394; Jayne, Ann. 216, 100; 

 Erdmann, Ann. 227, 258 ; Leoni, Ann. 

 256, 64). The latter on boiling with 

 water gives a-naphthol (Fittig and Erd- 

 mann, Ann. 227, 242), from which a- 

 naphthaquinone, and thence juglone 

 and hydrojuglone, can be obtained by 

 converting the naphthol into i :'4-nitro- 

 sonaphthol (a-naphthaquinoneoxime) by 

 the action of nitrous acid (2-nitroso- 

 I -naphthol is formed simultaneously) 

 (Fuchs, Ber. 8, 626 ; Ilinsky, Ber. 17, 

 2590 ; Henriques and Ilinsky, Ber. 18, 



706). The nitrosonaphthol reduces to 

 I : 4-aminonaphthol (Grandmougin and 

 Michel, Ber. 25, 972), and this can be oxi- 

 dised to a-naphthaquinone as under A. 



The azo-derivatives of a-naphthol also 

 give i : 4-aminonaphthol on reduction 

 (Liebermann and Jacobson, Ann. 211, 

 36; Seidel, Ber. 25, 423; Grandmougin 

 and Michel, loc. cit.}. a-Naphthyl ace- 

 tate gives some a-quinone on oxidation 

 (Miller, Ber. 14, 1600). 



[C.] From cinnamic and malonic acids 

 [Vol. II], and methyl alcohol [13]. Cin- 

 namic acid is converted into its methyl 

 ester and brominated so as to form the di- 

 bromide. The latter, when heated with 

 sodio-malonic methyl ester in methyl 

 alcohol solution, gives Fai-phenyltri- 

 methylene-2 : 2 : 3 - tricarboxylic tri- 

 methyl ester, from which the free acid 

 can be obtained by hydrolysis (Buchner 

 and Dessauer, Ber. 25, 1153). The acid 

 on heating (in CO 2 ) at 180-200, and 

 finally by distillation in a vacuum, yields 

 phenylisocrotonic acid (Ibid. 1 155), which 

 can be converted into a-naphthol, &c., 

 as under B. 



[D.] Furfural [126] and benzene [6] 

 give a-naphthylamine by heating pyro- 

 mucic acid (see under erythritol [50 ; 

 N"]) with aniline, zinc chloride, and 

 lime at 300 (Canzoneri and Oliveri, 

 Gazz. 16, 493). The naphthylamine 

 can be converted into a-naphthaquinone, 

 &c., as under A. 



[E.] Mannitol [5l] and benzene \Q\ 

 can be made to give a small quantity 

 of a-naphthylamine by heating the al- 

 cohol with aniline hydrochloride at 

 200-240 (Effront, Jahresber. 1885, 

 I2io ; Ber. 18, Ref. 383). 



[F.] From cinnamic aldehyde [123] 

 and hippuric acid [Vol. II], which con- 

 dense to form an anhydride which, by 

 the action of sodium hydroxide, gives 

 cinnamylidenehippuric acid [C 6 H g . CH : 

 CH . CH : C(COOH)NH . CO . C 6 H 5 ], 

 and this on heating with hydrochloric 

 acid to 1 1 o-i 20 yields (with a-naphthoic 

 acid) naphthalene (Erlenmeyer, junr., 

 and Kunlin, Ber. 35, 384). 



[G.] Pyrogallol [84] on oxidation gives 

 a product (purpurogallin) which yields 

 naphthalene on distillation with zinc dust 

 (Nietzki and Steinmann, Ber. 20, 1278). 



