Synthesis and Properties of N-(2,2,2-Trichloroethylidene)- and N-(2,2,2-Trichloroethyl)nitrobenzenesulfonamides

Highly reactive N-(2,2,2-trichloroethylidene)nitrobenzenesulfonamides were synthesized by reaction of N,N-dichloronitrobenzenesulfonamides with trichloroethylene. Reactions of N-(2,2,2-trichloroethylidene)nitrobenzenesulfonamides with oxygen and nitrogen nucleophiles gave products of addition at the double CÍN bond; with arenes and haloarenes, the corresponding C-amidoalkylation products were obtained.     

N-(2,2,2-Trichloroethylidene)- and N-(1-Hydroxy-2,2,2-trichloroethyl)amides in C-Amidoalkylation Reaction of Functionally-substituted Aromatic Compounds

A reaction with phenol and pyrocatechol of N-(2,2,2-trichloroethylidene)arenesulfonyl-, ethoxycarbonylamides and 1-hydroxy-substituted N-(2,2,2-trichloroethyl)amides of arenesulfonic, carbamic, and acetic acids in the presence of oleum or in sulfuric acid provided the corresponding (1-amido-2,2,2-trichloroethyl)-substituted phenols. N-(2,2,2-Trichloroethylidene)-4-chlorobenzenesulfonamide reacted with salicylamide in the presence of oleum to afford 3-aminocarbonyl-4-[2,2,2-trichloro-1-(4-chlorobenzenesulfonamido)ethyl]benzene whereas the 1-hydroxy-2,2,2-trichloroethylamides of the acetic, carbamic, and arenesulfonic acids did not enter into such reactions.     

Synthesis and Properties of N-(2,2,2-Trichloroethyl)-2-thiophenesulfonamides

Chlorination of 2-thiophenesulfonamide gave unstable N,N-dichloro-2-thiophenesulfonamide which was brought into reactions with 1,2-polyhaloethenes. The condensation of 2-thiophenesulfonamide with trichloroacetaldehyde afforded N-(2,2,2-trichloro-1-hydroxyethyl)-2-thiophenesulfonamide which reacted with benzene, toluene, 2-chlorothiophene, and phenol to form the corresponding N-(1-aryl-2,2,2-trichloroethyl)-2-thiophenesulfonamides. Under more severe conditions, the latter were converted into 1,1-diaryl-2,2,2-trichloroethanes. The reaction of N-(2,2,2-trichloro-1-hydroxyethyl)-2-thiophenesulfonamide with substituted arenes, including phenol, was regioselective: only the corresponding para-substituted products were obtained. Hydrolysis of N-[2,2,2-trichloro-1-(4-tolyl)ethyl]-2-thiophenesulfonamide yielded N-(2-thienylsulfonyl)-2-(4-tolyl)glycine.     

Synthesis and Properties of N-(2,2,2-Trichloroethylidene)trifluoromethanesulfonamide and Its Derivatives

The reaction of N,N-dichloromethanesulfonamide with trichloroethylene gave N-(2,2,2-trichloro- ethylidene)trifluoromethanesulfonamide which showed high reactivity toward oxygen- and nitrogen-centered nucleophiles, as well as in C-alkylation of aromatic compounds.     

Oxidation of N-(1-Hydroxypolychloroethyl)sulfonamides

N-(2,2,2-Trichloro-1-hydroxyethyl)- and N-(2,2-dichloro-1-hydroxy-2-phenylethyl)arenesulfonamides are oxidized with chromium(VI) oxide to give, respectively, N-(arylsulfonyl)trichloroacetamides and N-(arylsulfonyl)dichloro(phenyl)acetamides. Under analogous conditions N-(2,2,2-trichloro-1-hydroxyethyl)trifluoromethanesulfonamide is converted into 1,1,1-trichloro-2,2-bis(trifluoromethylsulfonylamino)ethane.     

Unusual Cyclization of N-(1-Aryl-1-chloro-2,2,2-trifluoroethyl)-N'-(p-tolyl)-carbodiimides in the Presence of Triethylamine

1-Aryl-1-chloro-2,2,2-trifluoroethyl)-N'-(p-tolyl)carbodiimides treated with triethylamine undergo intramolecular cyclization into 4-aryl-6-methyl-2-triethylammonio-4-trifluoromethyl-4-dihydroquinazolidines.     

Synthesis of 2-methyl-N-(2,2,2-trichloroethylidene)- and 2-methyl-N-(2,2,2-trichloroethyl)benzenesulfonamides from N,N-dichloro-2-methylbenzenesulfonamide and trichloroethylene

The reaction of N,N-dichloro-2-methylbenzenesulfonamide with trichloroethylene gave a new representative of highly electrophilic N-sulfonyl polyhaloaldehyde imines, 2-methyl-N-(2,2,2-trichloroethylidene) benzenesulfonamide. High reactivity of the product was demonstrated in the addition of water and 2-methylbenzenesulfonamide and reactions with benzene, toluene, anisole, thiophene, and 2-chlorothiophene. N,N-Dichlorobenzenesulfonamides and N,N-dichlorotrifluoromethanesulfonamide failed to react with 1,1,3,3,4,4-hexachlorobut-1-ene and 1,1,2,3,4-pentachlorobuta-1,3-diene under the conditions ensuring formation of N-(2,2,2-trichloroethylidene)arenesulfonamides from N,N-dichloroarenesulfonamides and trichloroethylene.     

An IR Study of the Structure of New Thiocarboxylic Acid N-(1-Arenesulfonamido-2-phenyl-2,2-dichloroethyl- and -2,2,2-trichloroethyl)amides

An IR study of thiocarboxylic acid N-(1-arenesulfonamido-2-phenyl-2,2-dichloroethyl- and -2,2,2-trichloroethyl)amides revealed intramolecular hydrogen bonds whose formation is accompanied by electron density delocalization and stabilization of conformations with quasiaromatic rings. Formation of chelate species was confirmed by AM1 calculations.     

Reactions of Aroxy- and Arylsulfanylacetic Acids and Their Esters with N-(2,2,2-Trichloro-1-hydroxyethyl)sulfonamides and -carboxamides

C-Amidoalkylation of aroxy- and arylsulfanylacetic acids and their methyl esters was effected by reaction with N-(2,2,2-trichloro-1-hydroxyethyl)sulfonamides and -carboxamides in the presence of methane- or trifluoromethanesulfonic acids as catalyst and solvent. The process is regioselective, and the substitution occurs at the para-position with respect to the heteroelement-containing group.     

Tris(2,2,2-trichloroethoxy)iron(III) complexes

Summary The preparation, magnetic moments, i.r., reflectance and⁵⁷Fe Mössbauer spectra of adducts of tris(2,2,2-trichloroethoxy)iron (III) complexes are reported. An alkoxybridged structure is supported by i.r. spectra.⁵⁷Fe Mössbauer spectra are explained in terms of two inequivalent sites in highspin iron(III) octahedral symmetry.Abbreviations Pic-O -picolineN-oxide - Ur urea - DMU N,N-dimethylurea - Suc succinimide - Diox dioxan - Bipy 2,2-bipyridine - Phen 1,10-phenanthroline     

Structure and proton-donor ability of N-(1-trifluoromethylsulfonylamino-2,2,2-trichloroethyl)-acrylamide

Quantum-chemical calculations (B3LYP/6-311G**) of N-(1-trifluoromethylsulfonylamino-2,2,2-trichloroethyl)acrylamide CF₃SO₂NHCH(CCl₃)NHC(O)CH=CH₂ (I) in the isolated state revealed four local minima corresponding to the conformers with the syn- and antiperiplanar orientation of the C=O and N-H bonds in the amide fragment, two of which containing the intramolecular C(O)NH…O=S or SO₂NH…O=C hydrogen bonds. Judged from the data of IR spectroscopy and dielectrometry, compound I in inert media exists predominantly in the form of conformer with antiperiplanar amide fragment and free NH group. Its self-associates in molecular crystals and solutions are formed by hydrogen bonds SO₂NH…O=C. Spectroscopic acidity of compound I determined as the value of Δν(NH) upon interactions with DMF in CCl₄ is higher than that of N-methyltrifluoromethanesulfonamide.     

Heterocyclizations of Functionalized Heterocumulenes with C,N- and C,O-Dinucleophiles: III.* Cyclization of N-(1-Aryl-1-chloro-2,2,2-trifluoroethyl)-N'-arylcarbodiimides with 3-Substituted 1-Phenylpyrazol-5-ones

Cyclization of N-(1-aryl-1-chloro-2,2,2-trifluoroethyl)-N'-arylcarbodiimides with 3-substituted 1-phenylpyrazol-5-ones yields 6-aryl-4-arylimino-1-phenyl-6-trifluoromethyl-1,4,5,6-tetrahydropyrazolo[4,3-e][1,3]oxazines.     

Ru(II)-Catalyzed rearrangement of 2-aryl-2-(phenylthio)penta-3,4-dienyl 2,2,2-trichloroacetimidates

[RuCl₂(p-cymene)]₂ efficiently catalyzes the rearrangement of 2-aryl-2-(phenylthio)penta-3,4-dienyl 2,2,2-trichloroacetimidate to afford (Z)-2,2,2-trichloro-N-(4-aryl-1-(phenylthio)penta-2,4-dien-2-yl)acetamide. Ru carbene is assumed as the reactive intermediate in this rearrangement.     

Synthesis of N-(5-Pyrazolyl) Schiff Bases Derived from Aryl Trifluoromethyl Ketones

5-Amino-1-aryl-4-methylpyrazoles readily add to methyl 1-aryl-2,2,2-trifluoroethylidenecarbamates to give the corresponding methyl 1-aryl-2,2,2-trifluoro-1-(5-pyrazolylamino)ethylcarbamates which undergo fragmentation at elevated temperature in the presence of an organic base to afford N-(5-pyrazolyl)-1-aryl-2,2,2-trifluoroethanimines.     

Heterocyclization of N-(1-chloro-2,2,2-trifluoroethylidene)carbamates with β-enaminoesters—a novel synthetic strategy to functionalized trifluoromethylated pyrimidines

A novel synthetic strategy to 4-trifluoromethyl substituted 2-oxo-1,2-dihydropyrimidine-5-carboxylates has been developed based on the cyclocondensation of β-enaminoesters with N-(1-chloro-2,2,2-trifluoroethylidene)carbamates.     

Diastereoselectivity-Switchable Gold-Catalyzed Formal [3+2]-Cycloadditions of N-2,2,2-Trifluoroethylisatin Ketimines with Yne−Enones

The unexpected gold-catalyzed formal [3+2]-cycloaddition of N-2,2,2-trifluoroethylisatin ketimines with 2-(1-Alkynyl)-2-alken-1-ones is reported. Both diastereomers of the corresponding cycloadducts were formed in moderate to excellent yields with excellent diastereoselectivities by switching the catalytic system from mono-gold to gold/silver bimetallic catalytic system. The practicality of this protocol is demonstrated by scale-up reaction and the transformations of the cycloadduct.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-Arylsulfonyl-α-thienylglycines from <Emphasis Type="Italic">N</Emphasis>-(2,2,2-Trichloro-1-thienylethyl)arenesulfonamides

Reactions of N-(2,2,2-trichloroethylidene)arenesulfonamides with thiophene, 2-chlorothiophene, and 2,5-dichlorothiophene, as well as of N-(2,2,2-trichloro-1-hydroxyethyl)arenesulfonamides with 2-chlorothiophene, lead to formation of the corresponding N-(2,2,2-trichloro-1-thienylethyl)arenesulfonamides. Alkaline hydrolysis of the latter occurs selectively at the trichloromethyl group to give N-arylsulfonyl-α-thienylglycines.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 93–96.Original Russian Text Copyright © 2005 by Aizina, Rozentsveig, Ushakova, Levkovskaya, Mirskova.     

N-(2,2,2-trinitroethyl)-N-polynitrohexaazaisowurtzitanes

Russian Chemical Bulletin - Synthetic procedures towards a series of new high energy N-(2,2,2-trinitroethyl) derivatives of polynitrohexaazaisowurtzitanes were elaborated; the properties of the...     

Synthesis of poly(phenyltrifluoroethoxyphosphazene) by direct reaction of trimethylsilyl azide with bis(2,2,2-trifluoroethyl) phenylphosphonite

The reaction between bis(2,2,2-trifluoroethyl) phenylphosphonite and trimethylsilyl azide at temperatures from 70 to 120°C provides a mixture of bis(2,2,2-trifluoroethoxy)phenylN-(trimethylsilyl) phosphoranimine and poly(phenyl-2,2,2-trifluoroethoxyphosphazene). The polymer is probably formed by phosphine azide intermediates because the phosphor-animine is thermally stable up to 200°C. The polyphosphazene is an amorphous stereo-random polymer with a glass transition temperature at ?31°C.     

Functionalization of highly electrophilic <Emphasis Type="Italic">N</Emphasis>-(2,2,2-trichloroethylidene)- and <Emphasis Type="Italic">N</Emphasis>-(2,2-dichloro-2-phenylethylidene) arenesulfonamides with dithiooxamide

Depending on the reactant ratio, dithiooxamide (ethanedithioamide) reacted as N-nucleophile or N,N′-binucleophile with highly electrophilic aldimines, N-(2,2,2-trichloroethylidene)- and N-(2,2-dichloro-2-phenylethylidene)arenesulfonamides, to give the corresponding mono- or bis-adducts, N-[2-polychloro-1-(arylsulfonylamino) ethyl]ethanedithioamides or N,N′-bis[2-polychloro-1-(arylsulfonylamino)ethyl]ethanedithioamides, in good yield.