Dicarboxylic acid hydrazides

Acylhydrazono ketones or l,2-bis(acylhydrazones) react with ammonia or ammonium acetate to give 1,2,4-triazines 2 in good yield.122,129a 6,362 In a few cases the 2-acylhydrazono ketones are first converted into the chloro azines 1 and then reacted with ammonia. Derivatives of dicarboxylic acid hydrazides yield l,m-alkanobis(l,2,4-triazines) in 52-71 % yield.1296... 

As a hybrid between the isoluminol-based assays described in Section 3.1.4 and the horseradish peroxidase-catalyzed, luminol-based assays described here, Gun-dermann et al have described a high quantum-yield naphthalene cyclic hydrazide (7-dimethylaminonaphthalene-l,2-dicarboxylic acid hydrazide) and its use in assays catalyzed by horseradish peroxidase (G20). 

G19. Gundermann, K.-D., Horstman, W., and Bergman, G., Constitution and chemiluminescence (II) synthesis and chemiluminescence of 7-dialkylaminonaphthalene-l,2-dicarboxylic acid hydrazide. Justus Liebig s Ann. Chem. 684, 127 (1965). 

Hydrazine Pyridazine-3,6-diol ring from dicarboxylic acid hydrazides... 

Diamines from dicarboxylic acid esters via dicarboxylic acid hydrazides s. 12, 573... 

Nevertheless the fluorescence efficiency of the substituted phthalate dianion is a decisive factor in luminol type chemiluminescence. Since one can expect that the carboxylates of higher condensed aromatic hydrocarbons would exhibit high fluorescence efficiencies, a series of naphthalene-, anthracene- and homologuous o-dicarboxylic acid hydrazides have been synthesized and their chemiluminescence investigated. In the tables in Appendix, p. 205 some of these hydrazides synthesized since 1968 are listed. 

Fig. 10. Chemiluminescence efficiency of naphthalene-1,2-dicarboxylic acid hydrazides as a function of alkalinity [12].

The fact that (sterically non-hindered) dialkylamino -benzene- or -naphthalene dicarboxylic acid hydrazides do not exhibit a strong decrease of chemiluminescence quantum yield beyond pH 11, is a consequence of the fact that compounds like (4) - (p. 80) - cannot form a tri-anion [34, 35]. 

N-methyl acridone fluorescence. Similarly, naphthalene-2,3-dicarboxylic acid hydrazide has a very low chemiluminescence efficiency (about 5 x 1(T ), and a mixture of this hydrazide with DP A (both KT M) yields no more light than does the hydrazide alone. 

There are, however, certain cyclic diacyl hydrazides which chemiluminesce very poorly in anhydrous DMSO as well as in water, but which, in mixed DMSO/ water solvents, yield a rather strong chemiluminescence, e.g. 3-(2-dialkyl-aminovinyl) phthalhydrazides (see Appendix, p. 205) [44] and trans-4- dialkyl-amino stilbene-2,3-dicarboxylic acid hydrazides [18]. 

Enzyme immunoassays for digoxin, thyroxine and insulin have been performed with horse radish peroxidase as a label. The antigen-antibody complex was treated with luminol or other related hydrazides, the most efficient being 7-dimethylamino naphthalene-1,2-dicarboxylic acid hydrazide (92) (cf. p. 80) [129]. 

N-Dialkylamino- derivatives of phthalhydrazide and of naphthalene-dicarboxylic acid hydrazides were found to have their highest 0cl at an alkalinity of 0.01 n NaOH (Ref. VIL9. [12]). 

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