Hydrazo compounds quinolines

Pyridine reacts with sodium hydrazide in the presence of hydrazine to yield 2-hydrazinopyridine in the absence of free hydrazine a hydrazo compound is formed (Scheme 88) (64AG(E)342). A difference between hydrazination and amination is the formation of 1,4-adducts which cannot be rearomatized even on heating. This is reflected in the behaviour of quinoline, which gives only a 0.5% yield of a -hydrazino product, whereas 4-methylquino-line is hydrazinated in 76% yield (64AG(E)342). Acridine behaves differently with sodium hydrazide/hydrazine, 9,10-dihydroacridine is formed almost quantitatively, but reaction in the absence of hydrazine yields 9-aminoacridine (65%). An even higher yield of 9-amino-acridine is obtained when sodium Af.AC-dimethylhydrazide is used (Scheme 89). Good evidence for intermediacy of (151) comes from the isolation of (152) on hydrolysis of (151). 

Via intermediates Quinolines and indoles from hydrazo compounds... 

Of the aromatic dibasic acids, the three phthalic acids on treatment with hydrazoic acid yield the corresponding aminobenzoic acids with mere traces of the diaminobenzenes. > Anthranilic acid and its derivatives in which one hydrogen on the amino group is replaced by acetyl, benzoyl, or p-toluyl are inert to hydrazoic acid. These compounds thus resemble in activity a-amino acids and their derivatives in the aliphatic series. The following pyridine and quinoline acids resemble -amino acids and also do not react pyridine-2-carboxylic acid, pyridine-2,3-... 

The study of the produets of the 2- and 4-(4 -azidostyryl)quinolines photolysis by the electrospr mass spectrometry showed that, as a result of the photodissoeiation of the N-N2 bond, a set of products typical of the azide photoehemistry were formed corresponding arrrines, rritroso, nitro, azo, hydrazo, and azoxy compounds (the last three in insigrriflcant amormts) [74], In the azide photolysis in the presenee of HCl, the ratio of these products changed, and the ehlorine-eontaining eompotmds were formed in addition. There were some produets, whieh eould not be identified by mass spectrometry. In addition, the formation of unsubstituted styrylquinolines was also detected. This finding indicated the photodissoeiation of the C-N3 bond, a proeess that is imeonventional in the photochemistry of aromatic azides. 

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