154 



EEPORT — 1901. 



Isomeric Bromo-^-Naphthols — continued. 



Bromo-derivative 



^'o. i. 



Br(?) 



Ex tetrabromo-/3-naph - 

 thol No. 2 and boil- 

 l. iug iodbydric acid. 



No. 1. 

 Br 



Br 



Ex /3-napbtliol in 

 glacial acetic acid 

 and excess of Br^ in 

 presence of iron. 



No. 2. 

 Br(?)Br 



Brl^/I^Br(?) 



By excess of Br^ on 

 dry ^-naphtbol at 

 100° in presence of 

 iron. 



No.Z. 



Formed along with 1 

 and 2 in small quan- 

 tity. 



No.\. 



By action of bromine 

 in excess on dry /3- 

 naphthol in pre- 

 sence of Al or Fe ; 

 also by bromine ou 

 tetrabromo, No. 2. 



iVo. 2. 



Ex tetrabromo-^-naph- 



thol, No. 1, by 



dropping into bro- 



\ mine coutainiug Al. 



Properties 



From acetic acid in flat, 



ejfiorescent needles 



(with 1 mol. C.H.O,) ; 



melts at 135-136°. 



Acetate, small leaflets 



ex ethyl acetate, m.p. 



147°. 



From acetic acid in 

 small balls of 

 needles {efflorescent), 

 m.p. 172°. 



Acetate, from ethylic 

 acetate in long, lus- 

 treless prisms, or 

 small six-sidtd plates, 

 m.p. 192-193°. 



From acetic acid or 

 chloroform in long 

 slender needles {non- 

 efflorescent), m.p. 

 184°. 



Acetate, from ethylic 

 acetate or acetone in 

 small dumbbell-like 

 aggregates of needles, 

 m.p. 155°. 



Small, colourless 

 needles from acetic 

 acid, m.p. 191°. 



Acetate, from acetic 

 acid (very sparingly 

 soluble) in felted 

 mass of needles, m.p. 

 210°. 



Tiny colourless needles 

 from nitrobenzene, 

 m.p. 241°. 



Acetate, ex ethylic ace- 

 tate, small needles, 

 m.p. 209°. 



Acetate, m.p. 203°, 

 white granules. 



Convertible by HNO3 

 into 



(1) 1 - Nitro -3:4:6- 

 tribromo-j3-naphthol, 

 dark yellow needles, 

 m.p. between 135- 

 143°, depending on 

 rate of heating. 



(2) 3 : 4 : 6-tribromo- 

 1:2- naphthaqui- 

 none, from ethylic 

 acetate in large, deep- 

 red nearly black 

 rhombs, m.p. 190°. 



(1) Nitro - tribromo - (3- 



naphthol, yellow tufts 

 from alcohol, m.p. 

 156° (decomposes). 



(2) Tribromo-jS-naph- 

 thaquinone from 

 etliylic acetate in 

 large red prisms, 

 m.p. 183°. 



Does not yield a keto- 

 compound initially 

 with HNO,, but gives 

 immediately a tetra- 

 bromo - fi • naphtha - 

 quinone, m.p. 241° 

 (small red needles). 



A tetrabromo-jS-naph- 

 thaquinone, m.p.l64°. 



Bemarks 



Does not etherify. 



Note close resemblance 

 of naphthols 3 and 4 

 and acetates S, 3, 

 and 4. 



Oxidation by dilute 

 HNOj converts the 

 naphthol and the 

 derived quinone into 

 4-bromophthalic acid; 

 anhydride, m.p. 106°. 



Oxidation of either 

 naphthol or quinone 

 gives a new dibromo- 

 phthalio acid, m.p. 

 195-196° ; anhydride, 

 m.p. 147-5°. 



Attempts at oxidation 

 hitherto unsuccessful. 



On oxidation yields 

 a tribromopbthalio 

 BCld.' 



' Flessa, Ber., 17, 1479. 



