DERIVATIVES OF HIGHLY SUBSTITUTED ANILINES. 179 XXI1.-Derivutives of Highly Substituted Anilines. By FREDERICK DANIEL CHATTAWAY and JOHN MELLO WADMORE. A NUMBER of acyl derivatives of the 2 : 4-dihalogen and the 2 : 4 : 6-tri- halogen anilines have been prepared during the last few years in the course of an investigation on the phenomena of intramolecular re- arrangement in aromatic amines, and their properties are here placed on record. The aniiides can be obtained by heating the substituted aniline with the equivalent amount of propionyl or benzoy 1 chloride. Vigorous action generally occurs a t 160-180°, and the heating is preferably con- tinued so long as hydrogen chloride is evolved. The product can be crys- tallised from either alcohol or a mixture of chloroform and petroleum.The nitrogen chlorides may all be prepared by adding an excess of a cooled solution of bleaching powder to the anilide dissolved in glacial acetic acid, complete conversion being ensured by extracting with chloroform and vigorously shaking the solution with fresh, slightly180 CHATTAWAY AND WADMORE : DERIVATIVES OF acidified calcium hypochlori te for some hours. The cliloroform solution, when dried over calcium chloride and evaporated in a current of dry air, yields the chloroamine derivative in the form of a viscid liquid which a t once solidifies on cooling and stirring with light petroleum, and can then be crystallised from petroleum or from a mixture of this solvent with a little chloroform, A pure anilide invariably yields a product which solidifies at once and crystallises readily in lustrous, well-shaped crystals ; whereas the presence of even a very small quantity of an admixed isomeride renders the product incapable of solidification.If such a mixture is dissolved in warm petroleum, no crystvls form on cooling, but a viscid, semi-solid mass separates, which only occasionally becomes partly crystalline. 4-Chloro- 6- b ~ o mo benxnrtilide, C,H,CIBr-NH CO*C6H5, separn tes from alcohol in slender, coloiarless prisms and melts at 130.5'. 0.2486 yielded 0.2662 mixed AgCl and AgBr. Halogen = 37.30. C,,H90NCIBr requires halogen = 37.17 per cent. The percentage of halogen throughout has been calculated on the assumption that silver chloride and silver bromide are present in the precipitate in the same proportion as the respective halogens in the anil ide.1 -BenzoyZchZoroami~ao-4 -c?~Zoro-6-b~omobenxene, C6H,ClBr*NC1*COPh, separated in colourless plates melting atl 62O. 0.5084 required 29.2 C.C. N/lO T. 4-Cl~Zoro-6-bromopropionaniZide, C,H,ClBr*NH*COEt, forms slender, 0.2332 yielded 0,2947 mixed AgCl and AgBr. C,H90XC1Br requires halogen = 43.95 per cent. 2-Ci~Zoro-4-b~omobenxaniZide, C,H,CIBr*NH*COPh, cryst allises f1 om alcohol in transparent, colourless, flattened prisms, and melts a t 1 4 5 O . C1 (as NCl) = 10.18. C,,H,ONCl,Br requires Cl (as NCl) = 10.28 per cent. colourless prisms and melts at 128.5". Halogen = 44.03. 0.1868 yielded 0.2007 mixed AgCl and AgBr. Halogen = 37.43. C,,H,ONClBr requires halogen = 37.17 per cent. 1-BenxoylchZo~oam~~ao-3-chZoro-4-bromob~nzene, C,H,ClBr*NCl*COPh, forms colourless plates melting a t 74".0.4294 required 24.7 C.C. N/10 I. C1 (as NCl)= 10.36. C,,H,ONCI,Br requires C1 (as NC1) = 10.28 per cent. 2 - C'ldoro - 4-~romopropionnni~i~e, C6H,C1Br cdourless, hair-like needles and melts at 129O. H *COEt, crys t allises inHIQKLY SUBSTI'CUTTED ANILINES. 181 0.2036 yielded 0.2581 mixed AgCl and AgBr. Halogen = 44.16. C,H90NClBr requires halogen = 43.96 per cent. C,H2Br3*NC1'COPh, which separates in glistening, coloiirless, rhombic plates with domed edges, melts at 1 1 5 O . 1 -BenzoyZchloroamino-Z : 4 ; 6-tribrornobenxene, 0.2368 required 10 C.C. n ; l l O I. C1 (as NCI) = 7.48. C,,HyONC1Br3 requires ctl (as NC1) = 7.57 per cent. 4-Chloro-2 : 6-dibrornobenznniZide, C,H,ClBr,*NH*COYh, forms trans- parent, colourless plates and melts at 194".0.21 14 yielded 0.2802 mixed AgCl and AgBr. Halogen = 49.88. CI,H,0NC1Br2 requires halogen = 50.16 per cent. 1 - Benxoy ZchZo~~oamino-4-ci~Ioro- 2 ; 6-dib*onaobenxene, C,H,C 1 Br;NCl*COP h, was obbained in short, colourless, transparent, four-sided prisms with domed ends melting at 111". 0.2352 required 11.1 C.C. N/lO I. C1 (as NC1) = 8-37. C,,H70NC1,Br, requires C1 (as NC1) = 8.36 per cent. 4-Chloro-2 : 6-dibromopropionanilide, C,H2C1Br;NH*COE t, separates in long, colourless, flattened prisms melting a t 185'. 02388 yielded 0.3646 mixed AgC1 and AgBr. Halogen = 57.45. C,H,ONCl Br, requires halogen = 57.21 per cent. 1 - Propiony Zchloroanaino-4-chloro-3 ; 6-dibromobenxene, C,H,CIBr,*NCl*COEt, forms slender, transparent, colourless prisms and melts at 74".0-2602 requires 13.7 C.C. N/10 I. C1 (as NC1) = 9.33. C,H70NC12Br2 requires C1 (as NCl) = 9.43 per cent. 2 : 6-DichZo?*o~4-bromobenxaniZide, C,H,Cl,Br*NH*COPh, crystallises i n short, colourless prisms and melts at 195'. 0.2448 yielded 0.3345 mixed AgCl and AgBr. Halogen = 43-43. C,,HsONC12Br requires halogen = 43.73 per cent. 1 -Be~zzoyZc?~Zoroc~mino-2 ; 6- dich Zoro-4-bronzo6enxene, forms transparent, colourless plates and melts at, 95". C6H2CI,Br*NCl*COPh, 0.2030 requires 10.7 C.C. N/lO I. C1 (as NCI) = 9.34. C,H?ONCl,Br requires C1 (as NCI) = 9-34 per cent.182 DERIVATIVES OF HIGHLY SUBSTITUTED ANILINES. 2 : 6-Dic~Zoro-4-bromopropionctnilid~, CdH,Cl,Br*NH*COEt, crystal- lises in colourless, flattened prisms melting at 184'.0.2418 yielded 0.3843 mixed AgCl and AgBr. Halogen = 50.51. C,H,ONCI,Br requires halogen = 50.80 per cent. 1-Benxoylchloroumino- 2 : 4-dichZoro-6-6~~omo6enxene, C,H,Cl, Br*NCl*COPh, forms transparent, colourless, f our-sided prisms with steeply domed ends and melts at 92O. 0.2204 required 11.7 C.C. N/10 I. C1 (as NCY) = 9.41. C1,H70NC13Br requires C1 (as NC1) = 9.34 per cent. '3 : 4-Dichloro- 6 - brom.o~ropionaniZide, C,H,Cl ,Br -NH CO E t , crystal- h e s in colourless needles and melts a t 165'. 0,2089 yielded 0.3338 mixed AgCl and AgBr. Halogen = 50.78. C,H,ONCl,Br requires halogen = 50.80 per ceu t. 2-Chloro-4 : 6-dib~omobenxaniZide, C,H,CiBr,*NH*COPh, which was obtained in colourless, short prisms terminated by pyramids, melts at 192O. 0.1704 yielded 0.2272 mixed AgCl and AgBr. Halogen = 50.17. C,,H,ONCIBr, requires halogen = 50.16 per cent. 1 - Benxo~ZchZoroan~ino-2-clilol.0-4 ; 6-dibromobenxene, C,H2C1Br2*NC1-COPh, separates in colourless, short, four-sided prisms with domed ends and melts at 9 7 O . 0.2240 requires 10-7 C.C. N/10 I. C1 (as NC1) = 8.46. Cl3H70NCI2Brl requires C1 (as KCl) = 8.36 per cent, 2-Chloro-4 : 6-dibromopropionanilide, C,H,CIBr,*NH°COEt, forms colourless needles melting at 185-5'. 0.1862 yielded 0.2828 mixed AgCl and AgBr. Halogen = 57.15. C9H80NCIBr2 requires halogen = 57.21 per cent. QT. B4RTHOLoMEW'8 HOSPITAL AND COLLEGE.