JACKSON, DUNLAP. — BROMINE DERIVATIVES OF RESORCINE. 229 



a state of undoubted purity for analysis. From their properties, 

 however, it can be inferred that they are substituted resorcine ethers 

 formed by a reaction involving the hydroxyl groups of the tribroni- 

 resorcine. Sodium malouic ester gave a similar unmanageable product 

 with tribromresorcine, but in addition to this acetylentetracarboxylic 

 ester was isolated. This substance could hardly be formed here other- 

 wise than by the action of brommalonic ester on sodium malonic ester, 

 and the brommalonic ester must have been formed by the replacement 

 by hydrogen of one or more atoms of bromine in the tribromresorcine. 

 It follows, therefore, that in this respect also the two hydroxyl radicals 

 behave like the two nitro groups in tribromdinitrobenzol, in which a 

 similar .replacement of bromine by hydrogen has been observed when 

 this substance is treated with sodium malonic ester. 



The tribromresorcine diethyl ether melts at 68° -69°, and is formed 

 by the action of an excess of bromine on the dibromresorcine diethyl- 

 ether, melting point 99°-100°. This latter substance is prepared by 

 the addition of bromine to a solution of resorcine diethylether in 

 glacial acetic acid. The tribrom product was shown to have the 

 bromine atoms in the symmetrical position to each other by treatment 

 with nitric acid, which converted it into the tribromnitroresorcine di- 

 ethylether melting at 101°, which is made from symmetrical tribrom- 

 trinitrobenzol. * The action of nitric acid on dibromresorcine diethyl- 

 ether was entirely different, as the product was a new dinitroresorcine 

 diethylether melting at 126°, formed by the replacement of the two 

 atoms of bromine by two nitro groups. A similar replacement of 

 bromine by nitro groups was observed when the tribromresorcine was 

 treated with fuming nitric acid, the product being the bromdinitro- 

 resorcine described by Typke f and Fevre. t As this substance was 

 obtained by the latter from dibromnitroresorcine, in this case also 

 bromine was replaced by a nitro group, and several other cases are 

 to be found in the chemical literature although they are far from 

 common. 



The most important point established by the observations given 

 above is that in these cases hydroxyl or ethoxyl radicals have the 

 same effect upon bromine which they have upon hydrogen attached 

 to the benzol ring; for just as phenols are much more susceptible to 

 the replacement of their hydrogen by halogens or nitro groups than 



* These Proceedings, XXV. 183. 



t Ber. d. ch. G., XVI. 555. 



t Bull. Cliem. Soc, XXXIX. 591. 



