Diazotization Of Aniline Halogenated Derivatives

In a wide variety of compounds,nitrogen-containing heterocyclic compounds as a majority of biological activity have become a class of eye-catching compounds. Many drugs,such as anti-cancer drugs,antibacterial drugs in both the molecular structure containing imidazole and indole ring.It is an important research field to synthesize these compounds and transform its structure.In this paper,a halogenated aniline as starting material,through diazotizated reaction,and ultimately synthesized four series of compounds,of which two series are triazoline-ketone and indole,the other two series are azo and hydrazone compounds.Work as follows:1.To fluorine,chlorine,bromine and other halogen substituted aniline as the guide, at a low temperature diazotization with sodium nitrite reaction occurred,and then stannous chloride reduction of halogenated intermediates phenylhydrazine hydrochloride.2.Halides phenylhydrazine hydrochloride at room temperature and pyruvate hydrazone reaction,and then with diphenyl azide phosphoric acid in toluene reflux 4-5h to form the 1 -(2 - fluoro -4 - bromophenyl) -3 - methyl-1H-1,2,4 -triazoline--one and 1 -(2,4 - dichlorophenyl) -3 - methyl-1H-1,2,4 - triazole Morpholine -5 - ketone,above prepared compounds reacted with CHCIF2 under certain conditions to form 1 -(2 - fluoro -4 - bromophenyl) -3 - methyl -- 4 -difluoro-methyl-1H-1,2,4 - triazoline--5 --one and 1 -(2,4 - dichlorophenyl) -3 -methyl -4 -difluoro-methyl-1H - 1,2,4 - triazoline--5 - ketone.In addition,the use of theophylline and the CHClF₂ under the same conditions by the product of difluoromethylation3.Halides phenylhydrazine hydrochloride in ethanol and pyruvic acid reflux, acid-catalyzed reaction of 5 - bromo--7 - fluoro-1H-indole -2 - ethyl and 5,7 -dichloro --1H-indole -2 - ethyl,and then with N,N-dimethylformamide in toluene reflux,phosphorus oxychloride reaction catalyzed by 5,7 - dichloro--3 - aldehyde-1H - indole -2 - ethyl and 5 - bromo--7 - fluoro -3 - aldehyde-1H-indole -2 - ethyl.In addition,the use of halogenated phenylhydrazine hydrochloride and cyclohexanone, 1,3 - diphenyl-1,3 - dione in ethanol,benzoyl suflfonic acid-catalyzed by the 6 -bromo--8 - F -2,3,4,9 - tetrahydro-1H-carbazole and 5 - bromo--7 - F -2 -phenyl-1H-indole -3 - benzophenone. 4.To fluorine,chlorine,bromine and other halogen substituted aniline as the guide, at 0℃below diazotization by sodium nitrite,and then with 1 - naphthalidine amine coupling reaction took place,by the three azo derivatives;to Halogenated aniline as the raw material,at 0℃below diazotization by sodium nitrite,and then by the stannous chloride reduction by phenylhydrazine hydrochloride,then with substituted benzaldehyde,acetophenone,pyruvic acid and other carbonyl compounds react has been replaced by seven aryl hydrazone compounds.All prepared compounds have been charactered by MS,IR,1H NMR.