368-66-1Relevant articles and documents
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McBee et al.
, p. 391 (1937)
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Norton
, p. 3527 (1950)
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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.
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.