UNSATURATED NITROGEN-COMPOUNDS CONTAINING FLUORINE .10. REACTION OF 2,5-DICHLORO-1,1,1,6,6,6,-HEXAFLUORO-3,4-DIAZAHEXA-2,4-DIENE WITH HALIDE ION AND OXYGEN- AND SULFUR-CENTERED NUCLEOPHILES AND OF ITS 2,5-DI-IODO ANALOG WITH REDUCING AGENTS AND CERTAIN NUCLEOPHILES

The azines CF(3)CR=NN=CRCF(3)(R=F, I, PhO, 2,4-Cl2C6H3O, PhS and EtO) are formed by treatment of the title dichloroazine 1 with an excess of the appropriate nucleophile, while reaction with phosphorus (V) sulphide at 180 degrees C gives 2,5-bis(trifluoromethyl)-1,3,4-thiadiazole in quantitative yield. In the reaction with NaOEt, the compound CF3C(OEt)=NN=C(ONa)CF3 is also produced from the NaOH impurity present. Di-iodoazine 3b undergoes ready reaction with aniline (1:2 molar ratio) and potassium diethyl phenylmalonate (1:1 molar ratio) to afford the monosubstituted compounds PhN=C(CF3)NHN=CICF3 and (EtO(2)C)(2)CPhC(CF3)=NN=CICF3, respectively. Azine 1 is not reduced by the reagents NaH, LiAIH(4), and NaBH4, but di-iodoazine 3b is reduced by tri-n-butyltin hydride at c. 90 degrees C to give mainly the compounds CF3CH=NN=CHCF3, CF3CH=NN=CICF3, CFCH2NHN=CICF3 and possibly CF3CH=NNHCH2CF3; with hydrogen iodide at 200 degrees C, the major products are the hydroazines CF3CH=NN=CHCF3 and CF3CH=NN=CICF3 and 2,4,6-tris(trifluoromethyl)-1,3,5-triazene.