368-66-1Relevant academic research and scientific papers
Formation of Urea, Isourea, and Triazine Derivatives from Diisopropylcyanamide with Trifluoroacetic Anhydride and Trifluoromethanesulfonic Anhydride: Thermal Instability of Urea and Isourea Derivatives
Norris, William P.,Merwin, Lawrence H.,Ostrom, Gregory S.,Gilardi, Richard D.
, p. 9070 - 9075 (2007/10/03)
Diisopropylcyanamide reacts exothermically with trifluoroacetic anhydride to give 2, an equilibrium mixture, in C6D6 solution, of 1:1 adducts, N,N-diisopropyl-N', O-bis(trifluoroacetyl)isourea, 2a (10%), and N,N-diisopropyl-N',N'-bis(trifluoroacetyl)urea, 2c (90%), at 27°C. Compound 2c is a colorless solid, mp 49-51°C. Thermolysis of 2, at 117°C, shows first-order kinetics with the intital products being trifluoroacetonitrile, 4, and diisopropylcarbamic trifluoroacetic mixed anhydride, 3. Trifluoroacetonitrile trimerizes to 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, and 3 is thermally labile giving diisopropyltrifluoroacetamide and CO2. In the thermolysis reaction 4 reacts with 2a to give a small amount of 4-(diisopropylamino)-4-(trifluoroacetoxy)-2,6-bis(trifluoromethyl)-4H-1,3,5- oxadiazine, 7. A related compound, 4,4-bis(diisopropylamino)-2,6-bis(trifluoromethyl)-4H-1,3,5-oxadiazine, 8, is formed from 7 and 2c going through a concentration maximum at 4000 s in the kinetic run. Compound 8 thermolytically dissociates to generate 4 and tetraisopropylurea. Compound 2 is a trifluoroacetylating agent with methanol giving methyl trifluoroacetate in 97% yield. Accompanying this reaction is a methanol displacement of diisopropylamine giving a 1.7% yield of methyl-N-(trifluoroacetyl)urethane. Diisopropylcyanamide also reacts exothermically with trifluoromethanesulfonic anhydride to give 2,4,6-tris(diisopropylamino)-l-(trifluoromethanesulfonyl)triazinium trifluoromethanesulfonate, 15, in 96% yield. X-ray crystallographic structure drawing of 15 shows N1 (attached to CF3SO2) is pyramidal while N2, N4, and N6 (all diisopropylamino nitrogens) are sp2-planar. A small amount of O-ethyl-N,N-diisopropyl-N'-(trifluoromethanesulfonyl)isourea was also recovered, produced by the reaction of the initially formed intermediate, N,N-diisopropyl-N',O-bis(trifluoromethanesulfonyl)isourea, with ethanol contaminant in absolute ethyl ether solvent. Treatment of 15 with methanol, in the presence of K2CO3, gave a 90% yield of 2,4,6-tris-(diisopropylamino)-1-(trifluoromethanesulfonyl)-4-methoxy-1,4- dihydrotriazine.
Unsaturated nitrogen compounds containing fluorine. Part 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 sulphur-centred nucleophiles and of its 2,5-di-iodo analogue with reducing agents and certain nucleophiles
Eltoum, Ahmed O. A.,O'Reilly, Neil J.,Tipping, Anthony E.
, p. 101 - 110 (2007/10/02)
The azines CF3CR=NN=CRCF3 (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 deg 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 (EtO2C)2PhC(CF3)=NN=CICF3, respectively.Azine 1 is not reduced by the reagents NaH, LiAlH4 and NaBH4, but di-iodoazine 3b is reduced by tri-n-butyltin hydride at c. 90 deg C to give mainly the compounds CF3CH=NN=CHCF3, CF3CH=NN=CICF3, CFCH2NHN=CICF3 and possibly CF3CH=NNHCH2CF3; with hydrogen iodide at 200 deg C, the major products are the hydroazines CF3CH=NN=CHCF3 and CF3CH=NN=CICF3 and 2,4,6-tris(trifluoromethyl)-1,3,5-triazene.
REACTION OF PERFLUOROTRIMETHYLAMINE WITH ANTIMONY PENTAFLUORIDE. SYNTHESIS AND X-RAY STRUCTURE OF A PERFLUORINATED HEXAHYDRO-TRIAZINEDIONE DERIVATIVE
Buerger, H.,Koeplin, R.,Pawelke, G.,Krueger, C.
, p. 175 - 184 (2007/10/02)
Perfluorotrimethylamine and SbF5 at an elevated temperature slowly eliminate CF4 to form the cation (III). (III) is also obtained from the reaction of CF3NCF2 with SbF5 in nearly quantitative yield.The hexahydrotriazinedione (IV) has been obtained by hydrolysis of (III).The constitution and structure of (IV) are established by X-ray crystallography.
Pressure-Induced Cyclotrimerization of Electron-Deficient Nitriles. Catalysis by Acidic Alcohols and Phenols
Koppes, William M.,Adolph, Horst G.
, p. 406 - 412 (2007/10/02)
Fluorodinitroacetonitrile (1) was pressurized at 1 GPa in the presence of a variety of ROH catalysts.Cyclotrimerization of 1 occurred in several cases, but the observed triazines contained RO groups in place of one or several CF(NO2)2 groups.Some mechanistic aspects of this reaction are explored by comparison with the results of the pressurization of preformed fluorodinitroacetimidates.
