King, F. E. published the artcileStructures of some supposed 2,4-azetidinediones. III. The “alloxan-5-o-dimethylaminoanil” of Rudy and Cramer, and its alkali hydrolysis product, Safety of 4-Bromo-N-methyl-2-nitroaniline, the publication is Journal of the Chemical Society (1951), 3080-5, database is CAplus.
o-Me2NC6H4NH2 (I) and BzH yield N-benzylidene-o-dimethylaminoaniline (II), viscous yellow oil, absorption maximum at 248 mμ, min. at 231 mμ (ε 16,500 and 13,100); cold dilute mineral acid yields BzH. I and alloxan-H2O (III), by the method of Rudy and Cramer (C.A. 32, 7041.6), yield 15% 1,1′,2,2′,3,3′,4,4′,5,6-decahydro-4′-methyl-[spiropyrimidine-5,2′-quinoxaline]-2′,4′,6′-trione (IV), C12H12N4O3, yellow, m. 250° (decomposition), absorption maximum at 217, 250, and 306 μ (ε 36,540, 7520, and 4500) and min. at 242 and 283 mμ (ε 7250 and 2275); IV results in 19% yield from the reactants in aqueous EtOH (3 days at room temperature) in the presence of a few drops of concentrated HCl; CH2N2 gives the di-N-Me derivative (V), C14H16N4O3, pale yellow, m. 194°, absorption maximum at 218, 250, and 306 mμ (ε 40,000, 7710, and 5030) and min. at 246 and 282 mμ (ε 7400 and 2280); V yields an Ac derivative, C16H18N4O4, m. 288°. III is the alloxan-5-o-dimethylaminoanil (VI) of R. and C. [Ann. 333, 37 (1904)]. p-Me2NC6H4NH2 and III in boiling EtOH give the p-isomer of VI, a nearly black powder, absorption maximum at 256 and 405 mμ (ε 26,400 and 7500) and min. at 225, 355, and 440 mμ (ε 13,240, 3820, and 5220). IV, boiled with 30% aqueous NaOH, gives 1,2,2′,3,4,4′-hexahydro -2′,4′-dioxo-4-methylglyoxalino [1′,5′:1,2]quinoxaline (VII), m. 240°; CH2N2 gives the 3′,4-di-Me analog (VIII) of VII, m. 154°, absorption maximum at 218, 260, and 307 mμ (ε 26,500, 8600, and 4700) and min. at 248 and 284 mμ (ε 7590 and 1930); picrate, chocolate-brown, m. 133°, unstable. VII was designated by R. and C. as mesoxalimide. VI and VII have a high degree of acid stability (cf. behavior of II) and the stability of VII to 50% aqueous NaOH or concentrated HCl argues against the proposed formulas of R. and C.; the p-isomer of VI is decomposed by acid. o-O2 NC6H4NMeSO2C6H4Me-p on reduction over Raney Ni at 20°/6 atm., gives 94% N-(o-aminophenyl)-N-methyl-p-toluenesulfonamide (IX), m. 107-8°. IX (62 g.), 37 g. ClCH2CONHCO2Et, and 27.7 g. PhNMe2, heated 6 hrs. at 120-30°, give 45% 1-[o-(N-methyl-p-tolylsulfonamido)phenyl]hydantoin (X), m. 268-70°, largely unchanged after 14 hrs. at room temperature with 90% H2SO4. The use of EtOH in the above reaction gives a poor yield of X, together with 8.5% N-[o-(N-methyl-p-tolylsulfonamido)phenyl]glycine Et ester, m. 150°. X, heated 1 hr. on a steam bath with H2SO4 in AcOH, gives 85% 1-(o-methylaminophenyl)hydantoin (XI), m. 224-6°; CH2N2 gives the 3-Me derivative (XII), m. 153-4°. X and MeI in Me2CO containing K2CO3, refluxed 36 hrs., give the 3-Me derivative, m. 134-5°; hydrolysis yields XII (Ac derivative, m. 187-8°). XI (4 g.), 17.5 g. HCO2Et, and 0.4 g. Na, heated 2 hrs. on a steam bath, give 85% 1,2′,4,4’tetrahydro-2′,4′-dioxo-3′,4-dimethylglyoxalino[1′,5′:1,2]quinoxaline (XIII), orange-yellow, m. 260°; XIII is not reduced by Na in boiling EtOH or catalytically. XIII (1.4 g.) in 20 cc. AcOH and 100 cc. concentrated HCl, heated 3 hrs. on a steam bath while 25 g. granulated Sn is added, and the filtrate (cooled in ice H2O) basified with 40% NaOH, gives 47% VIII (picrate, chocolate-brown, m. 133°). XI, HCO2Et, and Na, heated on the steam bath 1 hr. and kept 14 hrs., give 44% unchanged XI and 28% 1,2′,4,4’tetrahydro-2′,4′-dioxo-4-methylglyoxalino[1′,5′:1,2]quinoloxaline, yellow, m. 270°; reduction with Sn and HCl gives VII. XII (2 g.), 20 cc. AcOEt, and 0.4 g. Na, heated 5 hrs. on the steam bath, give 47% unchanged XII and 1,2′,4,4’tetrahydro-2′,4′-dioxo-3,3′,4-trimethylglyoxalino[1′,5′:1,2]quinoxaline, yellow, m. 190-1°. XII does not react with BzOEt and Na. BrCH2CO2Et (62 g.) and 103 g. o-O2NC6H4NH2 (XIII), heated 4.5 hrs. at 120-35°, give 52 g. XIII.HBr and 60% N-(o-nitrophenyl)glycine Et ester (XIV), yellow, m. 77-8°; XIV does not react with ClCO2Et (alone or with C5H5N); evaporation of XIV with concentrated HCl gives 90% o-O2NC6H4NHCH2CO2H, m. 190°. The acid or its ester did not yield (o-nitrophenyl)hydantoin. 3,4-Me2C6H3NH2 (XV) (43 g.) and 20 g. ClCH2CO2Et, heated 1 hr. at 100°, give 67.5% N-(3,4-dimethylphenyl)glycine Et ester (XVI), m. 49-50°. XV (21.2 g.) and 14.5 g. ClCH2CONHCO2Et give 70% 1-(3,4-dimethylphenyl)hydantoin (XVII), m. 206-7°; it results also from XVI and CO(NH2)2 at 150-60°. XVII with MeI and K2CO3 in Me2CO give 79% of the 3-Me derivative (XVIII), m. 169-70°; CH2N2 gives the same product. XVIII and HNO3-H2SO4 (10 min. at 0°) give 34% of a diNO2 derivative, m. 226°; XVIII and HNO3 in AcOH (14 hrs. at room temperature) give 10% of a mono-NO2 derivative, pale yellow, m. 130-2°. o-O2NC6H4NH2 and BrCH2COCO2Et (4 hrs. at 120-30°) give 35% 4,2-Br(O2N)C6H3NH2 (XIX); 7.5 g. XIII and 13.2 g. HO2CCOCHBrCO2Et (4 hrs. at 130-5°) give 5 g. XIX.
Journal of the Chemical Society published new progress about 53484-26-7. 53484-26-7 belongs to bromides-buliding-blocks, auxiliary class Bromide,Nitro Compound,Amine,Benzene, name is 4-Bromo-N-methyl-2-nitroaniline, and the molecular formula is C7H7BrN2O2, Safety of 4-Bromo-N-methyl-2-nitroaniline.
Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary