Synthesis of 1-(N-perfluoroalkanesulfonylamino)-2,2,2-(trichloroethyl)dialkylphosphonates and phosphonic Acids

Trifluoromethanesulfonamides and Related Compounds

“…Higher N , N -dichloroperfluoroalkanesulfonamides R F SO 2 NCl 2 were prepared similarly. , With the disodium salt of triflamide CF 3 SO 2 NNa 2 , N , N -dichlorotriflamide gives “chloramine-Tf” CF 3 SO 2 NNaCl . With an excess of trichloroethylene, N , N -dichloroperfluoroalkanesulfonamides give N-sulfonylated imines of chloral R F SO 2 NCHCCl 3 and pentachloroethane (cf. refs − ).…”

N-Functionally substituted imines of polychlorinated (brominated) aldehydes and ketones

“…For instance, when N,N-dichloronitrobenzenesulfonamide, aminobenzenesulfonamide and N,N-dichloroamides of perfluoroalkanesulfonic acids are made to react with trichloroethene (TCE), the chloral sulfonylimines 2e ± h are formed; 70,71 the reaction of N,N-dichlorourethanes with TCE affords chloral N-alkoxycarbonylimines 10a ± c in preparative yields. 72,73 The reactions of TCE with N,N-dichloroarenesulfonamides in the presence of Lewis acids (SnCl 4 , AlCl 3 ) also afford the sulfonylimines 2a ± c, which are formed, however, in lower yields (up to 47%); N-(1-arylsulfonylamino-2,2,2-trichloroethyl)arenesulfonamides are formed as side products.…”

“…Cl2CHC(CONH2)NHCOPh NHR It has already been mentioned (see Section II.7) that N-(2,2dichloro-1-cyanovinyl)benzenesulfonamide 50 reacts with amines with substitution of the cyano group to afford stable 1-amino-2,2dichloroethylideneamides 51a ± e. 103 It has also been found that N-(1-acyl-2,2-dichloroethylidene)benzenesulfonamides 54a ± c can exist as two tautomers; 104 the amide form predominates in the solid state, whereas in solutions the equilibrium shifts towards the imine form. The facts that the equilibrium is established over a relatively long period and that the tautomers can be observed separately indicate that the energy barrier separating these forms is higher than 107 kJ mol 71 . 104 It should be emphasised that bromination of the NH group in N-(1-tert-butoxycarbonyl-2-methyl-and 2-ethylvinyl)acetamides yields unstable compounds which undergo a 1,3-halotropic rearrangement with migration of the halogen atom giving rise to the imines 20a,b (see Section II.4).…”

“…The sulfonylimines 2a,b readily react with triethyl phosphite to give diethyl N-(2,2-dichlorovinyl)-N-(arylsulfonyl) phosphoramidates 98a,b in high yields. 71,146 Dialkyl N-trichloroethylidene phosphoramidates react with trialkyl phosphites giving rise to bis(phosphorylated) compounds 99. 147 The reactions of dialkyl N-tetrachloroethylidene phosphoramidates with trimethyl and triethyl phosphites occur in a similar way and result in the formation of trichlorovinylamides Cl 2 C=CClN[P(O)(OR 1 ) 2 ] (R 1 = R 2 = Me, Et; R 1 = Me, R 2 = Et).…”

“…149 Organophosphorus acids and thioacids react with imines to give addition products. 36,37,150,151 N-Acetyl-, 37 N-ethoxycarbonyl- 36 and perchloroalkylsulfonyl-trichloroacetaldimines 71 readily add various organophosphorus reagents. In the case of dialkyl phosphites, dialkyl 1-acetyl-, 1-ethoxycarbonyl-and perchloroalkylsulfonyl-amino-2,2,2-trichloroethylphosphonates 105 are formed.…”