2.4.6- Tris-trifluoromethyl-1,3,5-triazine

For the formation of 2,4.6-tris(difluoromethyl)- and 2.4,6-tris(trifluoromethyl)-1,3.5-triazine from 2,2-difluoro- and 2,2,2-trifluoroacetonitrile, respectively, see Flouben-Weyl, Vol. E9c. pp 678, 679. 

Tris (trifluoromethyl)-s-triazine Tris (pentafluoroethyl)-s-triazine Tris (heptafluoropropyl)-s-triazine Tris (perfluoroheptyl)-s-triazine Tris (perfluorononyl)-s-triazine Ultramark 1621 (fluoroalkoxy cyclotriphosphazine mixture)... 

Trifluoroacetonitrile 254 trimerizes to give 2,4,6-tris-(trifluoromethyl)-l,3,5-triazine 255 (Equation 34) <1997JOC9070>. 

The toxicity of 2,4,6-trifluoro-jy/n-triazine (cyanuric fluoride) has been quantified 2,4,6-tris(trifluoromethyl)-j> /n-triazine is considerably less toxic. A wide range of acyl fluorides may be obtained in high yields by treating the corresponding acids at 20 °C with cyanuric fluoride in acetonitrile in the presence of pyridine double bonds, hydroxy-groups, and aromatic nuclei are unaffected. ... 

Trifluoroacetaldehyde figures in recent work on the synthesis of analogues of nitramine-type explosives, having been used to prepare 2,2,2-trifluoro-1,1-dinitraminoethane (20) by application of the route used to procure Medina itself [CHj(NHNOj)2] (Scheme 19), and to obtain the 2,4,6-tris(trifluoromethyl) derivative (22) of RDX (Scheme 20). Nitration of 2,4,6-tris(trifluoromethyl)hexahydro-sym-triazine (21) yields the heterocyclic nitramine (22) directly. The acetamido-analogue [CF3-CH(NH COMe)2] of the bisformamide (19a) can be prepared by heating anhydrous trifluoroacetaldehyde with acetamide, and the trifluoroacetamido-compound... 

According to quantum-chemical calculations, the second pathway is preferable. Thus, 2,4,6-tris-trifluoromethyl-l,3,5-triazine 36 reacts readily with active electron-rich dienophile, 3-aminopyrrole 37, generated in situ, yielding 2,4-bis-(trifluoromethyl)-5H-pyrrolo[3,2-(f]pyrimidine 38. The electron-withdrawing trifluoromethyl groups facilitate the reaction which proceeds at room temperature giving an 85% yield of 38 (13JOC8614). 

Reactions of replacement of SMe [79], trichloromethyl [97] or trifluoromethyl groups represent effective approaches for modifications of trifluoromethyl containing 1,3,5-triazines. Direct vapor-phase fluorination of tris-(trifluoromethyl)-s-triazine 74 has been studied and was found that the perfluoroalkyl groups of 74 were progressively replaced by fluorine to give mixture of 2,4-difluoro-6-trifluoromethyl-s-triazine 156 and 2,4-bis-(trifluoromethyl)-6-fluoro-s-triazine 157 (Scheme 66) [98]. Photoirradiation of tris-(trifluoromethyl)-i-triazine in cyclohexane leads to a mixture of adduct 158 and dihydrocompound 159 (Scheme 66) [99]. 

Diamine compound 161 was obtained in the reaction of tris(trifluoromethyl)-s-triazine 74 with ammonia. The reaction was presumed to proceed through addition-elimination mechanism as shown at Scheme 67 from the fact that 1,4-adduct was obtained, when ammonia gas was bubbled into the ether solution of the s-triazine [100]. 

Scheme 67 Reaction of tris(trifluoromethyl)-s-triazine 74 with ammonia...

Transformation of diamino-derivative 161 to N-oxide 162 was reported via oxidation with peracetic acid [101]. 2,4,6-Tris-(trifluoromethyl)-l,3,5-triazine 74 reacts with ethanol an the presence of hydrochloric acid to form ethyl trifluoroacetate [62]. 

Triazido-1,3,5 -triazine, 1348 Trifluoromethyl azide, 0347 Triphenylmethyl azide, 3783 Tris(2-azidoethyl)amine, 2482 1,1,1 -Tris(azidomethy l)ethane, 1937 Vinyl azide, 0770... 

Tris[2-(oxoethyl(trimethylammonium)ethoxy) triazine tris[bis(trifluoromethyl)sulfonyl)imide]... 

Photolysis of 3,5,6-tris[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]-l,2,4-triazine gives 2,4,6-tris[l, 2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]-l, 3,5-triazine (1), perfluorobutane-nitrile, perfluoro(2,5-dimethylhex-3-yne) and nitrogen.304... 

Thermal and photochemical reactions of 1,3.5-oxa and thiadiazines are uncommon however, the thermolysis of 4,4-bis(diisopropylamino)-2,6-bis(trifluoromethyl)-4//-l,3,5-oxadiazine 71 has been reported (Scheme 8) < 1997JOC9070>. Compound 71 dissociates to tetraisopropylurea and trifluoroacetonitrile 72, which trimerizes to give 2,4,6-tris-(trifluoro-methyl)-l,3,5-triazine 73. Monomeric 72 is never detected. 

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