1H-1,2,3-triazole-4,5-dicarbonitrile synthesis

Yield:-

Reaction Conditions:

with sulfuric acid;sodium nitrite in water at 20 - 25; for 2 - 2.5 h;Product distribution / selectivity;

Steps:

1.2; 1

Step 2"; Synthesis of 4, 5-dicyanotriazolate silver; Into a flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser tube, a stirrer, and a dropping funnel, dicyanomaleonitrile (hereinafter, described as DAMN) 216 g (2.0 mol), sulfuric acid 98 g, and ion exchange water 400 g were charged. While the mixture was maintained at 0°C under nitrogen flow, sodium nitrile 138 g (2.0 mol) and water 400 g were added dropwise into the mixture over 1 hour.Then, the mixture was maintained at 25°C for 1 hour and then the reaction was completed.Then, the reaction solution was subjected to extraction step using diethyl ether and ion exchange water to obtain a brown solid. This obtained solid was sublimed at 80°C and at 30 Pa to obtain white 4, 5-dicyanotriazole (hereinafter, described as HDCTA) 16O g.; Production Example 1; Into a 2L-separable flask into which water 400 gwas charged, sulfuric acid 98 g (1 mol) and diaminomaleonitrile 216 g (2mol) were added sequentially. Under stirring with a paddle blade, the flask was in an ice bath and thereby the internal temperature was kept at 20⁰C. Simultaneously, an aqueous solution prepared by dissolving sodium nitrite 141.45 g (2.05 mol) in water 410 g was added dropwise over 2 hours. After completion of the dropwise addition, the stirring was continued for 30 minutes. The reaction liquid was subjected to suction filtration with a 0.2 μm mixed cellulose filter to remove insoluble contents therefrom. The obtained filtrate was dried and hardened with a rotating evaporator by removing moisture therefrom. Diisopropyl ether 400g was added to the obtained solid to extract dicyanotriazole therefrom. Then, water 400 g was added to the dicyanopropyl ether phase and thereby impurities causing coloring were washed. The solvent was removed from the diisopropyl ether solution of the dicyanotriazolewith a rotating evaporator. Thereby, HDCTA having a Hazen of 200 was obtained.

References:

WO2007/55392,2007,A1 Location in patent:Page/Page column 65-66; 72