4-Cinnolylhydrazine and its 3-chloro-, 6-chloro-, and 6-bromo-derivatives are described. Except for the 3-chloro-compound, these are oxidised by aqueous copper sulphate to the corresponding cinnolines. 4-Phenylhydrazino-and 3-chloro-4-phenylhydrazino-cinnoline have been prepared. Attempts to prepare derivatives of 3-aminocinnoline are mentioned, and miscellaneous quinoline derivatives reported.FROM the reaction between hydrazine and 4-chloroquinaldine Backeberg and Friedmann (J., 1938, 972) obtained either of two products, according to the conditions. Condensation in hot alcohol gave 4-quinaldylhydrazine, whilst reaction a t a higher temperature, under pressure, gave an isomeric compound which the authors suggested to be 3 : 4-diaminoquinaldine. Various pieces of evidence made this structure uncertain, but only after this work had begun was i t completely disproved (Koenigs and Freund, Ber., 1947, 80, 143).Since we desired to prepare 3 : 4-diaminocinnolinesJ in the light of Backeberg and Friedmann's suggestion it seemed _of interest to examine the reaction between 4-chlorocinnolines and hydrazine. Further, 4-cinnolylhydrazines offered the possibility of obtaining, by oxidation, hitherto unknown derivatives of cinnoline unsubstituted a t C,,,.4-Chlorocinnoline reacted with hydrazine in alcohol much more slowly and less vigorously than did 4-chloroquinazoline (Dewar, J., 1944, 619 ; we have repeated the reaction for
Herein, the synthesis, characterization and thermal behaviour of imidazole-based two copper-phosphate mixtures, A = Cu 2 (PO 4 )(OH)ÁCu(HPO 4 )(H 2 O)Á(C 3 H 4 N 2 ) 2 . 3.25 H 2 O and B = Cu 3 (PO 4 ) 2 H 2 OÁ(C 3 H 4 N 2 ) 3 (H 2 O)Á0.1(C 3 H 4 N 2 ).3.25 H 2 O are reported. The characterization was done by adopting various electro-analyticaltechniques such as elemental analysis, X-ray Powder Diffraction (XRD), Thermogravimetric Analysis (TGA) and Derivative Thermogravimetry (DTG), Fourier Transform Infrared (FT-IR) Spectrometry, Absorption Spectrophotometry and Ultraviolet-Visible and near Infrared (UV-Vis-NIR). Differential Scanning Calorimetry performed with the heating rate 10 K/min from 297.96 to 770.46 K in normal atmosphere for both mixtures. DSC data indicated that both mixtures A and B are exhibiting exothermic property by their net specific heat capacities (C p ) −11.11 and −2.83 J/g K, respectively. Therefore, these complex mixtures can be utilized as heat dissipation materials. Both mixtures A and B undergo phase change in terms of hydrated phase to dehydrated phase up to 356 and 392 K, respectively. The specific heat capacity of Mixture A during hydration, C p = 2.54 J/g K, is higher than the tin, lead, stainless steel, glass and aluminium at their respective melting points. This mixture is also found better than the commercial product based on lithium ion battery in terms of specific heat capacity. From UV-Vis-NIR analysis, it is found that the mixtures A and B are showing semiconducting behaviour with band gaps 1.66 and 1.68 eV, respectively. The average crystallite sizes of these nano-complex mixtures are 35.29 and 30.94 nm and these were calculated using the Debye-Scherrer equation and Williamson-Hall method.
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