120672-75-5Relevant articles and documents
Kinetics and mechanism of reaction between N-polyfluorophenylcarbonimidoyl dichlorides and tertiary amines in acetonitrile
Mikhailov,Savelova,Popov,Petrova,Platonov
, p. 1116 - 1124 (2003)
The reaction of N-polyfluorophenylcarbonimidoyl dichlorides with tertiary amines in acetonitrile afforded chloroamidines R2NC(Cl)=NAr F and alkyl chloride. The precursor of the products is the corresponding quaternary ammonium salt [R3N+C(Cl)=NAr F]-Cl-. The rate of the salt formation is described by a second order equation; however with some amines a saturation effect was observed for the reaction rate with the growing amine concentration. This fact and also the influence of the amine and the substrate structure on the reaction rate suggests that reaction proceeds by addition-elimination mechanism with formation of a tetrahedral intermediate. The latter in the rate-limiting stage undergoes a stereomutation into an intermediate of a configuration favorable for conversion into a quaternary salt.
REACTIONS OF N-POLYFLUOROPHENYLCARBONIMIDOYL DICHLORIDES WITH PRIMARY AND SECONDARY AMINES. KINETICS AND MECHANISM. SYNTHESIS OF POLYFLUORINATED CABODIIMIDES, CHLOROFORMAMIDINES, GUANIDINES AND BENZIMIDAZOLES
Kolesnikova, I. V.,Petrova, T. D.,Platonov, V.E.,Mikhailov, V. A.,Popov, A. A.,Savelova, V.A.
, p. 217 - 246 (2007/10/02)
The reactions of N-polyfluorophenylcarbonimidoyl dichlorides with primary and secondary aliphatic and aromatic amines have been studied.With primary aliphatic amines, the reactions led to carbodiimides or guanidines, depending on the amount of amine.The carbodiimides obtained reacted with amines to form guanidines.The reactions with primary aromatic amines produced only triarylguanidines.N-Pentafluorophenylcarbonimidoyl dichloride (I) reacted with tetrafluoro-o-phenylene diamine to give 2-pentafluoroanilino-4,5,6,7-tetrafluorobenzimidazole.Polyfluorinated benzimidazole derivatives were also produced by the thermolysis of polyfluorinated triarylguanidines.Heating of N1,N2,N3-tris(pentafluorophenyl)guanidine with K2CO3 in dimethylformamide led to 1,2,3,4,7,8,9,10-octafluoro-5-pentafluorophenyl-5H-benzimidazobenzimidazole.N-Polyfluorophenylcarbonimidoyl dichlorides reacted with various secondary amines alredy at room temperature giving N-polyfluorophenylchloroformamidines in high yields.Elevated temperature and prolonged reaction time led to formation of N-polyfluorophenylguanidines.Kinetics and mechanism of the reactions of N-polyfluorophenylcarbonimidoyl dichlorides with primary and secondary amines in acetonitrile at 25 deg C have been studied.The reactions have been found to proceed by a bimolecular nucleophilic addition-elimination mechanism via a tetrahedral intermediate.Possible reasons of formation of different products in the above transformations are discussed in terms of this mechanism.
