JACKSON AND CALVERT. METAPHENYLENE DIAMINE. 137 



gives bromdiamidobenzolsulphonic acid.* Dibromdinitroplienylma- 

 lonic ester gives bromamidoxiiidol,| nitrite of bromdinitrophenjlmalouic 

 ester gives amidoxyoxindol.J Brorauitrophenol gives amidophenol, 

 and bromnitrauisol gives amidoanisol.§ Metabromorthonitrobenzoic 

 acid and its isomeric form botb give authrauilic acid,|| and Hiibuer^ 

 also states that he obtained small quantities of orthophenylene dia- 

 mine from nitroparabromauiline, but that the principal product was 

 the bromphenylene diamine ; this, however, seems to be the only case 

 observed, and none are recorded to our knowledge in the para series. 

 We could find no record of the removal of other halogens under these 

 conditions, until Schlieper published a second paper** (after our work 

 on tribromdiuitrobenzol was finished), in which he describes the reduc- 

 tion of chlor- and ioduitropheuols or anisols, when he found that iodine 

 was removed just as bromine was, but that chlorine was not replaced 

 by hydrogen. On the other hand he found that bromine could not be 

 removed from derivatives of ortho- or paranitrophenols, as was to be 

 expected from the work of previous observers. From his experiments 

 he infers that bromine or iodine is replaced by hydrogen under the influ- 

 ence of tin and hydrochloric acid, when it stands in the ortho position 

 to the two negative groups (OH. Br. NOj- 1, 2, 3), although he has 

 not yet succeeded in bringing an absolute proof that this is the constitu- 

 tion of the substances with which he worked. 



Our experiments proved that when tribromdinitrobenzol was treated 

 with a mixture of tin, hydrochloric acid, and a little alcohol,tt all three 

 of the atoms of bromine were replaced by hydrogen, the product being 

 metaphenylene diamine. Schlieper's inference given in the preceding 

 paragraph, therefore, is not of general application, as, if this were the 

 case, only one atom of bromine would have been removed from the 

 tribromdinitrobenzol, since only one of them is in the ortho position 

 to both of the nitro groups, the constitution of this substance being 

 Br. NO^. Br. NOg. Br. H. It is to be observed also that the con- 

 version of unsymmetrical brommetadinitrobenzol into metaphenylene 



* Baessmann, Ann. Chem. CXCI. 244. 

 t Jackson ami Bancroft, tliese Proceedings, XXIV. 299. 

 I Jackson and Bentley, these Proceedings, XXVI. 95. 

 § Schlieper Ber. d. ch. G., 1892, p. 552. 

 II Hiibner Petermann, Ann. Chem. CXLIX. 135. 

 1[ Ann. Chem. CCIX. 3G0. 

 ** Ber. d. ch. G., XXVI. 2465. 



tt Sclilieper used stannous chloride and hydrochloric acid in his work, and 

 it is possible tliat tliis difference may have modified the result. 



