Formation of unexpected products in the attempted aziridination of styrene with trifluoromethanesulfonyl nitrene

The reaction of styrene with trifluoromethanesulfonyl nitrene generated from trifluoromethanesulfonamide in the system (t-BuOCl+NaI) results in the formation of trifluoro-N-[2-phenyl-2-(trifluoromethylsulfonyl)aminoethyl]methanesulfonamide, 1-phenyl-2-iodo-ethanol, and 2,5-diphenyl-1,4-bis(trifluoromethylsulfonyl)piperazine rather than the expected product of aziridination, 2-phenyl-1-(trifluoromethylsulfonyl)aziridine. The mechanism of the reaction is discussed.     

Electronic structure and basicity of trifluoro-N-methyl-N-(2-phenylethenyl)methanesulfonamide

The electronic structures and basicities of trifluoro-N-methyl-N-(2-phenylethenyl)methanesulfonamide, N-methyl-2-phenylethenamine, trifluoro-N-methylmethanesulfonamide, and their C-, N-, and O-protonated forms and H-complexes were studied at the B3LYP/6–311+G** and MP2/cc-pVTZ levels of theory. The basicity of the double bond in trifluoro-N-methyl-N-(2-phenylethenyl)methanesulfonamide is much lower than that in N-methyl-2-phenylethenamine, and its protonation is possible only in trifluoromethanesulfonic acid.     

Cyclization of trifluoro-<Emphasis Type="Italic">N</Emphasis>-(prop-2-yn-1-yl)methanesulfonamides to <Emphasis Type="Italic">N</Emphasis>-(hydroxymethyl)-1,2,3-triazoles

Three-component heterocyclizations of trifluoro-N-(prop-2-yn-1-yl)methanesulfonamide, trifluoro-N-pheny-N-(prop-2-yn-1-yl)methanesulfonamide, and trifluoro-N,N-di(prop-2-yn-1-yl)methanesulfonamide with formaldehyde and sodium azide afforded N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-, N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-N-phenyl-, and N,N-bis{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}trifluoromethanesulfonamides as the major products together with minor 1-(hydroxymethyl)-1H-1,2,3-triazole isomers.     

Reactions of trifluoromethanesulfonamide with amides and paraformaldehyde

Two- and three-component condensations of paraformaldehyde with trifluoromethanesulfonamide, acetamide, trifluoroacetamide, 1H-benzotriazole, methanesulfonamide, and malonamide were studied. N-Hydroxymethyl derivatives of trifluoroacetamide and 1H-benzotriazole reacted with trifluoromethanesulfonamide to give N-(trifluoroacetylaminomethyl)- and N-(1H-benzotriazol-1-ylmethyl)-substituted derivatives of tri-fluoromethanesulfonamide, as well as N,N′-methylenebis(trifluoromethylsulfonamide) and N-(trifluoromethyl-sulfonylaminomethyl)trifluoroacetamide as transamination products. Three-component condensation of trifluoromethanesulfonamide with paraformaldehyde and methanesulfonamide led to the formation of 1-methylsulfonyl-3,5-bis(trifluoromethylsulfonyl)hexahydro-1,3,5-triazine, and the reaction of trifluoromethanesulfonamide with paraformaldehyde and malonamide gave 4,10-bis(trifluoromethylsulfonyl)-2,4,8,10-tetraazaspiro-[5.5]undecane-1,7-dione whose structure was proved by X-ray analysis.     

Reaction of trifluoromethanesulfonamide with alkenes and cycloocta-1,5-diene under oxidative conditions. Direct assembly of 9-heterobicyclo[4.2.1]nonanes

Reactions of trifluoromethanesulfonamide with α-methylstyrene, 2-methylpent-1-ene, and cycloocta-1,5-diene in the system t-BuOCl-NaI were studied. In the reaction with α-methylstyrene 1-iodo-2-phenylpropan-2-ol was the only isolated product. The reaction with 2-methylpent-1-ene gave a mixture of N,N′-(2-methylpentane-1,2-diyl)bis(trifluoromethanesulfonamide), trifluoro-N-(2-hydroxy-2-methylpentyl)-methanesulfonamide, and N,N′-[oxybis(2-methylpentan-2,1-diyl)]bis(trifluoromethanesulfonamide). Trifluoromethanesulfonamide reacted with cycloocta-1,5-diene to produce a mixture of 2,5-diiodo-9-(trifluoromethylsulfonyl)-9-azabicyclo[4.2.1]nonane and 2,5-diiodo-9-oxabicyclo[4.2.1]nonane; this reaction may be regarded as the first example of direct assembly of bicyclononane skeleton.     

Comparison of the reactivity of N‐(p‐toluenesulfonyl)‐sulfinimidoyl fluorides and chlorides toward triphenylphosphine

The path of the reaction of aryl‐N‐(p‐toluenesulfonyl)‐sulfinimidoyl fluorides and triphenylphosphine is highly dependent on the order of the reactants addition. Addition of triphenylphos‐phine to aryl‐N‐(p‐toluenesulfonyl)‐sulfinimidoyl fluorides results in the formation of triphenyl(aryl‐thio)phosphonium salts of N,N′‐bis(p‐toluenesul‐fonyl)aryl‐sulfinamidines and triphenyldifluorophosphorane. By changing the reagent addition order, we obtained triphenyldifluorophosphorane, P,P,P‐triphenyl‐N‐(p‐toluenesulfonyl)‐phosphine imide, and diaryl disulfides. The outcome of the reaction aryl‐N‐(arenesulfonyl)‐sulfinimidoyl chlorides and triphenylphosphine does not depend on the order of addition of the reactants. P,P,P‐Triphenyl‐N‐(arenesulfonyl)‐phosphine imides, triphenyldichloro‐phosphorane, and diaryl disulfides were formed as a result. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:66–71, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20408     

Palladium–Schiff base–triphenylphosphine catalyzed oxidation of alcohols

Novel palladium(II)‐N‐(2‐pyridyl)‐N′‐(5‐R‐salicylidene) hydrazine triphenylphosphine complexes were synthesized and characterized by UV, IR, ¹H NMR and ³¹P NMR spectral analysis, C, H, N analysis and magnetic susceptibility measurements. The complexes were effective in the catalytic oxidation of primary and secondary alcohols in presence of N‐methyl‐morpholine‐N‐oxide as oxidant. The oxidation reactions were carried out in dichloromethane. A mechanistic study of the above reactions has been proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

Formation of 2,6-diphenyl-1,4-bis(trifluoromethylsulfonyl)piperazine in the reaction of styrene with trifluoromethylsulfonylnitrene

The reaction of styrene with trifluoromethylsulfonylnitrene generated in the system t-BuOCl-NaI led to the formation of trifluoro-N-[2-phenyl-2-(trifluoromethylsulfonylamino)ethyl]methanesulfonamide CF₃SO₂NHCH(Ph)CH₂NHSO₂CF₃, 2-iodo-1-phenylethanol, and heterocyclization product, 2,6-diphenyl-1,4-(trifluoromethylsulfonyl)piperazine. The latter is regioisomeric to 2,5-diphenyl-1,4-(trifluoromethylsulfonyl)-piperazine obtained previously by analogous reaction in the system t-BuOCl-NaI · 2 H₂O.     

Reactivity of arylnitroso oxides to triphenylphosphine

The kinetics of reactions between phenylnitroso oxide, 4-CH₃O-, 4-CH₃-, or 4-Br-phenylnitroso oxide and triphenylphosphine in acetonitrile at 295 ± 2 K were studied using pulsed photolysis. Only trans-nitroso oxides enter this reaction. The rate constants of the reaction increase with increasing electron-acceptor properties of the substituent in the aromatic ring of nitroso oxide; they are on the order of 10⁵ to 10⁶ l mol⁻¹ s⁻¹. The extinction coefficient for trans-4-methylphenylnitroso oxide at 420 nm was estimated at 3.9 × 10³ l mol⁻¹ cm⁻¹.     

Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

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.     

Conformations and Self-association of Trifluoro-N-(3-formylcyclohept-2-en-1-yl)methanesulfonamide

The structure of trifluoro-N-(3-formylcyclohept-2-en-1-yl)methanesulfonamide and its self-association in solution have been studied by IR spectroscopy and quantum chemical methods [B3LYP/6-311G(d,p), AIM]; proton affinities of basic centers in its molecule have been evaluated. Trifluoro-N-(3-formylcyclohept-2-en-1-yl)methanesulfonamide in inert solvents forms cyclic dimers, whereas in crystal chain associates are more likely to be formed via hydrogen bonding between the NH and C=O groups of neighboring molecules. The carbonyl group in the title compound undergoes protonation only by the action of very strong trifluoromethanesulfonic acid. Weaker acids give rise to solvate H-complexes at the NH, C=O, and S=O groups. The topology of hydrogen bonds in dimers of different types has been analyzed in terms of the AIM theory.     

Reaction of polyperoxides with triphenylphosphine

The triphenylphosphine deoxygenation of the polyperoxides, poly(styrene peroxide), poly(methyl methacrylate peroxide), and poly(α-methylstyrene peroxide) proceed via the phosphorane intermediates, which in the presence of moisture hydrolyze to give the respective diols. At higher temperatures and under dry conditions the phosphorane decomposes into epoxide and triphenylphosphine oxide. The reaction has been studied by ¹H-, ¹³C-, and ³¹P-NMR spectroscopy. The results obtained are consistent with a concerted insertion of the biphile, triphenylphosphine, into the peroxy bond and this reaction pathway seems to be new as far as the chemistry of polyperoxides is concerned. Though the aim of this investigation was to test the selective deoxygenation of polyperoxide by triphenylphosphine as a method of preparing polyethers, it turned out to be a fruitful method of synthesis of stereospecific diols. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1167–1172, 1997     

Condensation of Trifluoromethanesulfonamide with Paraformaldehyde and Oxamide

Depending on the conditions, three-component condensation of trifluoromethanesulfonamide with paraformaldehyde and oxamide led to the formation of linear products, N-mono- and N,N’-bis[(trifluoromethylsulfonyl)aminomethyl]oxamide, bis[(trifluoromethylsulfonyl)aminomethyl] ethanedioate, as well as of hydrolysis and cyclization product, N-(4,5-dioxo-1,3-oxazolidin-3-ylmethyl)trifluoromethanesulfonamide.     

Reaction of γ-dicarboxylic acids amides and imides with trifluoromethanesulfonamide and formaldehyde

Three-component condensation of trifluoromethanesulfonamide with paraformaldehyde and succinamide depending on the reaction conditions led alongside bis(trifluoromethanesulfonamido)methane to the formation of a substitution product, bis[(trifluoromethylsulfonyl)aminomethyl]succinamide, or to a cyclization product, N-[trifluoromethylsulfonyl)aminomethyl]succinimide. The attempt to obtain the latter by the reaction of the trifluoromethanesulfonamide sodium salt CF₃SO₂NHNa with N-chloromethylsuccinimide unexpectedly resulted in N,N-bis(succinimidomethyl)-trifluoromethanesulfonamide. Analogously the reaction of CF₃SO₂NHNa with N-chloromethyl-phthalimide gave N,N-bis(phthalimidomethyl)trifluoromethanesulfonamide. The reaction of CF₃SO₂NHNa with succinimide and phthalimide in water and alcohol solution resulted in the ring opening and further transformation of the formed monosubstituted N-(trifluoromethylsulfonyl)amides of succinic and phthalic acids.     

Special features of the interaction of pyridine and quinoline derivatives, and related compounds with triphenylphosphine

Using pyridine, quinoline, and related compounds as examples, it has been shown that their interaction with triphenylphosphine occurs via different pathways. Reaction of triphenylphosphine with N-vinylisonicotinic acid chloride leads to the mixture of 1,2-bis(triphenylphosphoniumchlorido)ethane and 4-carboxy-2-(triphenylphosphoniumchloridoethyl)pyridine. In the case of α-(N-2-carboxyquinolinylbromido)-β-bromopropionic acid, the reaction with triphenylphosphine proceeds via phosphine attack on the oxygen atom with elimination of quinaldinic acid, and subsequent nucleophilic substitution with the formation of 3-(triphenylphosphoniumbromido) propionic acid bromide.     

Synthesis of hydroxyphosphoranes from triphenylphosphine and triphenylphosphine oxide

Novel hydroxyphosphoranes were synthesized using the oxidative method from triphenylphosphine, 1,1′-dihydroxydicyclohexyl, benzopinacol, and aminophenol in the presence oftert-butyl hydroperoxide. Hydroxyphosphoranes were also obtained from triphenylphosphine oxide, and the series of dihydric phenols and diols mentioned above. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1779–1781, October, 1993.     

Synthesis and structure of <Emphasis Type="Italic">N</Emphasis>-(diaminomethylidene)- and <Emphasis Type="Italic">N</Emphasis>-[bis(cyclohexylamino)methylidene]trifluoromethanesulfonamides

N-Trifluoromethylsulfonyl-substituted guanidines CF₃SO₂N=C(NHR)₂ (R = H, cyclohexyl) were synthesized in nearly quantitative yield by reactions of N-sulfinyltrifluoromethanesulfonamide CF₃SO₂N=S=O with urea and of trifluoromethanesulfonamide with N,N′-dicyclohexylcarbodiimide. N-[Bis(cyclohexylamino)-methylidene]trifluoromethanesulfonamide was subjected to protonation with trifluoromethanesulfonic acid and bis(trifluoromethanesulfonyl)imide, and the structure of the resulting salts and initial N-trifluoromethylsulfonylguanidines was studied by NMR and IR spectroscopy and DFT quantum-chemical calculations.     

Structure and proton-donating ability of trifluoro-<Emphasis Type="Italic">N</Emphasis>-(2-phenylacetyl)methanesulfonamide

According to the data of quantum-chemical calculations and IR spectroscopy the trifluoro-N-(2-phenylacetyl)methanesulfonamide CF₃SO₂NHC(O)CH₂Ph in the isolated state and in inert media exists in the form of two conformers with the syn- and antiperiplanar orientation of the C=O and N-H bonds. Its self-associates in the CCl₄ solution and in molecular crystals constitute cyclic dimers formed by the NH···O=S bonds and chain dimers with the NH···O=C bonds. As a hydrogen bond donor, trifluoro-N-(2-phenylacetyl)methanesulfonamide is stronger than N-methyltrifluoromethanesulfonamide. Its pK _a in methanol is 5.45, that is 5 pK units lower than for amides CF₃SO₂NHR and 2 pK units higher than for imide (CF₃SO₂)₂NH.     

Kinetic study of triphenylphosphine addition to para‐benzoquinone

Kinetics of the addition reaction of triphenylphosphine to para‐benzoquinone in 1,2‐dichloroethane as solvent was studied. Initial rate method was used to determine the order of the reaction with respect to the reactants. Pseudo‐first‐order method was also used to calculate the rate constant. This reaction was monitored by UV‐vis spectrophotometry at 520 nm by variable time method. On the basis of the obtained results, the Arrhenius equation of this reaction was obtained: The activation parameters, E_a, ΔH^#, ΔG^#, and ΔS^# at 300 K were 5.701, 6.294, 19.958 kcal mol^?1 and ?45.853 cal mol^?1 K^?1, respectively. This reaction is first and second order with respect to triphenylphosphine and para‐benzoquinone, respectively. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36:472–479, 2004