The dichloroazine 5 has been converted into the monoaminoazines CF₃C(NHR)=NN=CClCF₃ (6) [a, R = Ph (89%); b, R = H (81%); c, R = Me (89%); d, R = CH₂CO₂Me (96%); e, R = CH₂CO₂Et (95%)] and the diaminoazines CF₃C(NHR) = NN = C(NHR)CF₃ (4) [c, R = H (96%); d, R = Me (94%); e, R = CH₂CO₂Me (50%); f, R = CH₂CO₂Et (77%)] by reaction with ammonia or the appropriate primary amino compound; with hydroxylamine the syn-oxime CF₃CCl = NNHC(CF₃) = NOH (8) (86%) was formed. The mixed diaminoazines CF₃C(NHR) = NN = C(NHR′)CF₃ (4) [g, R = H, R′ = Ph; h, R′ = Me, R′ = H; i, R = Me, R′ = CH₂CO₂Me; j, R = CH₂CO₂Me, R′ = Ph (92%–96%)] have been synthesised from the monoaminoazines 6a-d. A solution of the diaminoazine 4c, heated in ethanol under reflux, gave 3,5-bis(trifluoromethyl)-1H,2,4-triazole (1a) (28%) and its ammonium salt NH₄⁺[C₂N₃(CF₃)₂]⁻ (7b) (54%), while the azines 4g and 4j under the same conditions each afforded 4-phenyl-3,5-bis(trifluoromethyl)-4H-1,2,4-triazole (2c) (ca. 85%). Thermolysis of the diaminoazines 4c-f and 4h in vacuo over the range 120–150 °C gave the following results: 4c → 7b (98%); 4d → MeNH₃⁺ [C₂N₃(CF₃)₂]⁻ (7c) (ca. 26%)+Me₄N⁺ [C₂N₃(CF₃)₂]⁻ (7d) (ca. 13%) + 4-methyl-3,5-bis(trifluoromethyl)-4H-1,2,4-triazole (2b) (54%) + 1-methyl-3,5-bis(trifluoromethyl)-1H-1,2,4-triazole (1b) (1.5%); 4e → the 4-carbomethoxymethyltriazole (2e) (93%); 4f → the 4-carboethoxymethyltriazole (2f) (82%); 4h → 1a (11%) + 2b (54%) + 7c (31%). Treatment of salt 7b with aqueous hydrochloric acid afforded the triazole 1a (75%).

中文翻译：

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含氟的不饱和氮化合物。第16部分。由2,5-二氯-1,1,1,1,6,6,6-合成3,5-双（三氟甲基）-1 H -1,2,4-三唑和一些4-取代的衍生物六氟-3,4-二氮杂六-2,4-二烯

二氯嗪5已经转化为单氨基嗪CF ₃ C（NHR）＝ NN ＝ CClCF ₃（6）[a，R ＝ Ph（89％）； n ＝ 1。b，R ＝ H（81％）；c，R = Me（89％）；d，R ＝ CH ₂ CO ₂ Me（96％）；e，R ＝ CH ₂ CO ₂ Et（95％）]和二氨基嗪CF ₃ C（NHR）＝ NN ＝ C（NHR）CF ₃（4）[c，R ＝ H（96％）；e，R ＝H（96％）。d，R ＝ Me（94％）；e，R ＝ CH ₂ CO ₂ Me（50％）；f，R = CH ₂ CO ₂ Et（77％）]与氨或适当的伯氨基化合物反应；与羟胺的合成-肟CF ₃ CCl = NNHC（CF ₃）=生成NOH（8）（86％）。混合的二氨基嗪CF ₃ C（NHR）= NN = C（NHR'）CF ₃（4）[g，R = H，R'= Ph; h，R'= Me，R'= H；i，R ＝ Me，R′＝ CH ₂ CO ₂ Me；j，R = CH ₂ CO ₂ Me，R'= Ph（92％–96％）]是由单氨基嗪6a-d合成的。将二氨基嗪4c的溶液在乙醇中加热回流，得到3,5-双（三氟甲基）-1 H，2,4-三唑（1a）（28％）及其铵盐NH ₄ ⁺ [C ₂ N ₃（CF ₃）₂ ] ^-（7b）（54％），而在相同条件下的嗪4g和4j各自提供4-苯基-3,5-双（三氟甲基）-4 H -1,2,4-三唑（2c）（约85 ％）。二氨基嗪4c-f和4h在真空中于120–150°C范围内的热解得到以下结果：4c→7b（98％）；4d→MeNH ₃ ⁺ [C ₂ N ₃（CF ₃）₂ ] ^-（7c）（约26％）+ Me ₄ N ⁺ [C ₂ N ₃（CF ₃）₂ ] ^-（7d）（约13％） ％）+ 4-甲基-3,5-双（三氟甲基）-4 H-1,2,4-三唑（2b）（54％）+ 1-甲基-3,5-双（三氟甲基）-1 H -1,2,4-三唑（1b）（1.5％）; 4e→4-碳甲氧基甲基三唑（2e）（93％）; 4f→4-羧乙氧基甲基三唑（2f）（82％）; 4h→1a（11％）+ 2b（54％）+ 7c（31％）。用盐酸水溶液处理盐7b，得到三唑1a（75％）。