ChemInform Abstract: REACTION OF TRIBROMOETHYLENE WITH N,N‐DICHLOROBENZENESULFONAMIDE

Abstract

Die Reaktion der Titelverbindungen (I) und (II) führt unter Halogenabspaltung zu dem Produkt (III), das in der syn‐ und in der anti‐Form vorliegt, wie aus 1H‐NMR‐Daten zu schließen ist.

Polychloroethyltrifluoromethylsulfonamides from N,N-dichlorotrifluoromethylsulfonamide and dichloroethenes

“…In contrast to imine 4, the arenesulfonylimines of polyhaloaldehydes interact with phenol to give N-(1-phenoxy-2-polychloroethyl)amides, 7 whereas N- [1-(4-hydroxyphenyl)ethyl]amides are produced in the presence of oleum. 8 No diarylethanes like 11 were found.…”

“…8 No diarylethanes like 11 were found. 7,8 † NMR spectra were measured on a Bruker DPX-400 spectrometer. 1 H (400.13 MHz) and 13 C NMR (101.61 MHz) in [ 2 H 6 ]DMSO.…”

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

“…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. 74 It has been reported previously 23 that TCE reacts with N,Ndibromobenzenesulfamide or N,N-dibromourethane giving rise to the corresponding imines of 2-bromo-2,2-dichloroacetaldehyde BrCl 2 CCH=NSO 2 Ph and BrCl 2 CCH=NCOOMe.…”

“…According to quantum-chemical calculations, anti-isomer A is more favourable than syn-isomer B; this is confirmed by experimental and theoretical 35 Cl NQR data. 105 It has been shown by NMR spectroscopy that the dibromochloroacetaldehyde imines 12 and 55 exist as mixtures of syn-and anti-isomers in 3 : 4 107 and 1 : 3 76 ratios, respectively. Indeed, the 1 H NMR spectrum of the imine 55 exhibits, in addition to the multiplet for the phenyl protons, two singlets at 8.30 and 8.40 ppm due to the protons at the double bond, the ratio of their intensities being 3 : 4.…”

“…The 13 C NMR spectrum contains two signals for the carbon atoms of the CH=N group (167.9 and 167.6 ppm) and the CClBr 2 group (135.7 and 135.6 ppm). 107 More evidence supporting the existence of syn-and anti-isomers of imines is provided by the fact that addition of nucleophiles at the C=N bond affords two enantiomers. 107 It should be noted that syn-and anti-isomers cannot be detected in the 1 H NMR spectra of chloral sulfonylimines 2a ± c or ethoxycarbonylimines 10b, 108,73 dichloroacetaldehyde sulfonylimines 13a ± c or ethoxycarbonylimines 15, 76,77 or bromodichloroacetaldehyde sulfonylimines 17a,b or alkoxycarbonylimines.…”