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Preparation and thermal reactivity of hydrazinium 2,n-pyridinedicarboxylates (n = 3, 4, 5 and 6)

机译:Preparation and thermal reactivity of hydrazinium 2,n-pyridinedicarboxylates (n = 3, 4, 5 and 6)

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摘要

Hydrazinium 2,n-pyridinedicarboxylates of general composition N_2H_5HA, (N_2H_5)_2A·H_2O and N_2H_5HA·H_2A, where H_2A = 2,n-pyridinedicarboxylic acid (n = 3, quinolinic acid; n = 4, lutidinic acid; n = 5, isocinchomeronic acid and n = 6, dipicolinic acid) have been prepared by the neutralisation of aqueous solution of hydrazine hydrate with the respective acids, in stoichiometric ratios. Formation of these hydrazinium derivatives has been confirmed by analytical, IR spectral and thermal studies. Among these, the monohydrazinium salts are anhydrous whereas the dihydrazinium salts are monohydrated. While lutidinic and dipicolinic acids form all the three types of salts, the quinolinic and isocinchomeronic acids do not form N_2H_5HA·H_2A and N_2H_5HA, respectively, except the other two types. Infrared spectra of these salts reveal N-N stretching frequencies of the hydrazinium ion in the region 970-950 cm~(-1). The simultaneous TG and DTA of these salts show that all of them decompose without clear melting and lose hydrazine endothermically between 200 and 280 ℃, except dihydrazinium isocinchomeronate monohydrate in which half of the hydrazine molecule is lost exothermically, to give pyridinemono- or dicarboxylic acid intermediate which further decomposes exothermically to gaseous products.

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