Über Chalkogenolate. 184. Bis(thiocarbamoyl)- und Bis(N-methylthiocarbamoyl)sulfane

On Chalcogenolates. 184. Bis(thiocarbamoyl)- and Bis (N-methylthiocarbamoyl)sulfanes The sulfanes (H₂N? CS? )₂S₂ and (CH₃? NH? CS? )₂S_x with x = 1 and 2 have been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra. The decomposition of the N-methyl substituted compounds has been studied kinetically at 20°C in ethanolic solution.     

Über Chalkogenolate. 182. Bis(methoxythiocarbonyl) sulfane

On Chalcogenolates. 182. Bis(methoxythiocarbonyl)sulfanes The title compounds (CH₃O? CS? )₂S_x, where x = 1–4, have been prepared by different procedures. Their electron absorption, infrared, nuclear magnetic resonance, and mass spectra are reported.     

Über Chalkogenolate. 181 [1]. Thiocarbamoyl-methylsulfane

On Chalcogenolates. 181. Thiocarbamoyl Methyl Sulfanes The thiocarbamoyl methyl sulfanes H₂N? CS? S_x? CH₃? NH? CS? S_x? CH₃, and (CH₃)₂N? CS? S_x? CH₃ with x = 1 and 2 have been prepared by known procedures (for x = 1) and by reaction of the corresponding dithiocarbamate with the S-methylester of methanethiosulfonic acid CH₃? SO₂? SCH₃ (for x = 2). The compounds have been studied by means of diverse spectroscopic methods.     

Über Chalkogenolate. 180. Methoxythiocarbonyl-methylsulfane CH3O?CS?Sx?CH3 mit x = 1, 2 und Methylthiothiocarbonyl-methylsufane CH3S?CS?Sx?CH3 mit x = 1, 2

On Chalcogenolates. 180. Methoxythiocarbonyl Methyl Sulfanes CH₃O? CS? S_x? CH₃ with x = 1, 2 and Methylthiothiocarbonyl Methyl Sulfanes CH₃S? CS? S_x? CH₃ with x = 1, 2 The monosulfanes have been prepared by known procedures. For the first time the disulfanes have been synthesized by reaction of K[S₂C? OCH₃] and K[S₂C? SCH₃] with the S-methyl ester of methanethiosulfonic acid CH₃? SO₂? SCH₃. The sulfanes CH₃O? CS? S_x? CH₃ and CH₃S? CS? S_x? CH₃, where x = 1 and 2, have been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra.     

Über Chalkogenolate. 198. Untersuchungen über Polythiocuprate (I) [Cu(Sx)]− 2. Hydrazinium- und Ethylendiammoniumpolythiocuprate(I)

On Chalcogenolates. 198. Studies on Polythiocuprates(I) [Cu(S_x)]^?. 2. Hydrazinium and Ethylenediammonium Polythiocuprates(I) The red polythiocuprates(I) 1–5 (formulae see ?Inhaltsübersicht”?) have been prepared by reaction of hydrazinium or ethylenediammonium polysulfides with copper(II) salts, dissolved in water, under variable conditions. Their properties are described. In aqueous alkaline media 1–5 decompose into CuS and S; in the presence of carbon disulfide CuS, S_x^2?, and CS₃^2? besides CS₄^2? and S₂CO^2? are formed. The existence of the discreet ion [Cu₂CS₇]^2?, described in literature, was not confirmed. The polythiocuprates(I) 1–5 , dissolved im dimethylformamide, decompose via the radical anion S₃^?. The decomposition of S₃^? has been studied kinetically by means of compound 5 . The half-life of decay of S₃^? is τ_1/2 = 71.5 h at 20°C. The pentathiocuprate(I) 3 reacts with n-butyl chloride to produce the substituted sulfanes (C₄H₉)₂S_x′ where x = 1, 2 and 3.     

Über Chalkogenolate. 197. Untersuchungen über Polythiocuprate(I) [Cu(Sx)]− 1. Eigenschaften und Reaktionen von Ammoniumtetrathiocuprat(I)

On Chalcogenolates. 197. Studies on Polythiocuprates(I) [Cu(S_x)]^?. 1. Properties and Reactions of Ammonium Tetrathiocuprate(I) The properties of NH₄[Cu(S₄)] have been studied. In watery alkaline media it decomposes into CuS and S; in the presence of carbon disulfide CuS, S_x^2?, and CS₃^2? besides CS₄^2? and S₂CO^2? are formed. The compound (NH₄)₂[Cu₂CS₇], described in literature, does not exist. In dimethylformamide dissolved NH₄[Cu(S₄)] decomposes via the radical anion S₃^?. NH₄[Cu(S₄)] reacts with n-butyl chloride to yield the substituted sulfanes (C₄H₉)₂S_x with x = 1, 2, and 3.     

Difluoro(aryl)(perfluoroalkyl)‐λ4‐sulfanes and Selanes: Missing Links of Trichloroisocyanuric Acid/Potassium Fluoride Chemistry

The TCICA/KF approach to oxidative fluorination of heteroatoms has emerged as a surprisingly simple, safe, and versatile surrogate to classically challenging fluorination reactions. Although polyfluorination (or chlorofluorination) of diaryl disulfides, diaryl diselenides, diaryl ditellurides, aryl iodides, and aryl(perfluoroalkyl)tellanes has been described, the application of this TCICA/KF methodology to aryl(perfluoroalkyl)sulfanes and selanes remains an area of unexplored chemical space. Accordingly, to address the “missing links” in the developing series of chalcogen‐based substrate reactivity, we report mild syntheses of metastable difluoro(aryl)(perfluoroalkyl)‐λ⁴‐sulfanes and selanes. As only limited examples of these species exist in the current literature (accessible only by using F₂ or XeF₂/HF), we have carried out detailed structural analyses, primarily using NMR and SC‐XRD data. In addition, we investigate the effect of the perfluoroalkyl chain on the outcome of oxidative fluorination, and, finally, we provide preliminary evidence that difluoro(aryl)(trifluoro‐methyl)‐λ⁴‐sulfanes may act as fluorinating reagents.     

Über die Darstellung der Bis(triphenylsilyl)-sulfane (C6H5)3Si?Sx?Si(C6H5)3 (x = 3, 4) und die Kristallstruktur von (C6H5)3Si?S4?Si(C6H5)3

On the Preparation of Bis(triphenylsilyl)sulfanes (C₆H₅)₃Si? S_x? Si(C₆H₅)₃ (x = 3, 4) and the Crystal Structure of (C₆H₅)₃Si? S₄? Si(C₆H₅)₃ The preparation of the bis(triphenylsilyl)sulfanes Ph₃Si? S_x? SiPh₃ (x = 3, 4) from Ph₃SiSNa and SCl₂ resp. S₂Cl₂ is reported. They are characterized by vibrational, NMR and UV-VIS spectroscopic measurements. Ph₃Si? S₄? SiPh₃ crystallizes in space group P1 with a = 943.6(6) pm, b = 945.7(5) pm, c = 1 881.7(12) pm, α = 82.11(5)°, β = 78.95(5)°, γ = 83.15(5)° and Z = 2.     

Über Chalkogenolate. 185. Bis(N,N-dimethylthiocarbamoyl)sulfane

On Chalcogenolates. 185. Bis(N, N-dimethylthiocarbamoyl)sulfanes The title compounds have been synthesized by partial known methods. The sulfanes have been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra.     

Über Chalkogenolate. 123. Untersuchungen über N-Cyanomonothiocarbimidsäure. 3. O,S-Dimethylester der N-Cyanomonothiocarbimidsäure. Thiolyse und Hydrolyse des Esters

On Chalcogenolates. 123. Studies on N-Cyanomonothiocarbimic Acid. 3. O, S-Dimethyl Ester of N-Cyanomonothiocarbimic Acid. Thiolysis and Hydrolysis of this Ester (H₃CO)(H₃CS)C?N? CN has been prepared by reaction of K₂[SOC?N? CN] · H₂O with H₃CI. The thiolysis of this ester gives (H₃CO)(H₃CS)C?N? CS? NH₂. The acid hydrolysis forms (H₃CO)(H₃CS)C?N? CO? NH₂ via [(H₃CO)(H₃CS)C?N? C?NH]Cl. All compounds have been characterized by diverse methods.     

Über Chalkogenolate. 201. Untersuchungen über Selenformamide

On Chalcogenolates. 201 Studies on Selenoformamides The yellow selenoformamides H? CSe? NH₂, H? CSe? NH? CH₃, and H? CSe? N(CH₃)₂ have been prepared by reaction of the corresponding formamide with P₂Se₅. The compounds have been characterized by means of electron absorption, infrared, and nuclear magnetic resonance spectra. The decomposition of the selenoformamides in ethanolic solution has been studied kinetically at 20.0°C. The preparation of selenoformyl dithiocarbamates was not successful.     

S‐((Phenylsulfonyl)difluoromethyl)thiophenium Salts: Carbon‐Selective Electrophilic Difluoromethylation of β‐Ketoesters, β‐Diketones,and Dicyanoalkylidenes

S‐((Phenylsulfonyl)difluoromethyl)thiophenium salts were designed and prepared by a triflic acid catalyzed intramolecular cyclization of ortho‐ethynyl aryldifluoromethyl sulfanes. The thiophenium salts were found to be efficient as electrophilic difluoromehtylating reagents for introduction of a CF₂H group to sp³‐hybridized carbon nucleophiles such as of β‐ketoesters and dicyanoalkylidenes. The (phenylsulfonyl)difluoromethyl group can be readily transformed into CF₂H under mild reaction conditions. Enantioselective electrophilic difluoromethylation was also achieved in the presence of bis(cinchona) alkaloids.     

S‐((Phenylsulfonyl)difluoromethyl)thiophenium Salts: Carbon‐Selective Electrophilic Difluoromethylation of β‐Ketoesters, β‐Diketones,and Dicyanoalkylidenes

S‐((Phenylsulfonyl)difluoromethyl)thiophenium salts were designed and prepared by a triflic acid catalyzed intramolecular cyclization of ortho‐ethynyl aryldifluoromethyl sulfanes. The thiophenium salts were found to be efficient as electrophilic difluoromehtylating reagents for introduction of a CF₂H group to sp³‐hybridized carbon nucleophiles such as of β‐ketoesters and dicyanoalkylidenes. The (phenylsulfonyl)difluoromethyl group can be readily transformed into CF₂H under mild reaction conditions. Enantioselective electrophilic difluoromethylation was also achieved in the presence of bis(cinchona) alkaloids.     

Über Chalkogenolate. 122. Untersuchungen über N-Cyanomonothiocarbimidsäure 2. Kalium-S-methyl-N-cyanomonothiocarbimat und S-Methyl-N-cyanomonothiocarbimidsäure

On Chalcogenolates. 122. Studies on N-Cyanomonothiocarbimic Acid. 2. Potassium S-Methyl N-Cyanomonothiocarbimate and S-Methyl N-Cyanomonothiocarbimic Acid The reaction of K₂[SOC?N? CN] · H₂O with H₃CI gives K[O(H₃CS)C?N? CN]. The potassium salt reacts with acid to form (HO)(H₃CS)C?N? CN and with H₃CO? CO? Cl to yield (H₃CO? CO? O)(H₃CS)C?N? CN. The compounds have been characterized by means of spectroscopic methods.     

Über Chalkogenolate. 127. Diester der Cyaniminodiameisensäure NC?N(CO?OR)2 mit R = CH3, C2H5 und C6H5. Thiolyse der Diester

On Chalcogenolates. 127. Diesters of Cyanimino Diformic Acid NC? N(CO? OR)₂, where R = CH₃, C₂H₅, and C₆H₅. Thiolysis of these Diesters The diesters NC? N(CO? OR)₂ have been prepared by reaction of the sodium salt of cyanamide with the corresponding chloroformic acid ester. The thiolysis of these esters yields H₂N? CS? NH? CO? OR. The compounds with R = CH₃, C₂H₅, and C₆H₅ have been characterized by means of diverse methods.     

Über Chalkogenolate. 100. Untersuchungen über Monothiocarbamidsäure. 2. S-Methyl- und O-Methylmonothiocarbamat, 2,4,5-Trioxo-thiazolidin-(1,3)

On Chalcogenolates. 100. Studies on Monothiocarbamic Acid. 2. S-Methyl and O-Methyl Monothiocarbamate, 2,4,5-Trioxo-thiazolidine-(1,3) The methyl esters of monothiocarbamic acid H₂N? CO? SCH₃ and H₂N? CS? OCH₃ as well as 2,4,5-trioxo-thiazolidine-(1,3) and its potassium salt have been prepared and characterized by means of electron absorption, infrared, ¹H-NMR, and mass spectra.     

Mass spectra of some isopropyl benzene derivatives. A study of the ortho effect

The mass spectra of a series of ortho, meta and para substituted isopropyl benzene derivatives have been determined where the second substituent is ? COOH, ? C(O)NH₂, ? C(O)C₆H₅, ? C(Ph)(=NPh) or ? CH(Ph)(NHPh). Two bis-isopropylbenzophenones have also been studied. The spectra are characterized by prominent ortho effects which distinguish the ortho derivatives from the meta and para.     

α,ω-Bis(Dialkylthiophosphoryl)Sulfanes-Products of the Alcoholysis of Sulfur-Rich Phosphorus Sulfides

Abstract

The high solubility of sulfur-rich phosphorus sulfides in CS₂-especially in the range S:P=2.7 to 4-is the motive for new investigations on this system. DEMARCQ¹ suppsed the existence of “molecular products”, but he coulds not prove it by spectroscopic and chemical methods. As we have found the formation of α, ω-bis (fluorodithicphosphoryl) oliqosulfanes at the nucleophilic degradation of phosphorus sulfides with fluorides gives no proof for the existence of oligosulfane bridges in the sulfur-rich phosphorus sulfides. On the reaction of P₄S₁₀, elementary sulfur and alka-lifluorides the same products are formed. Sulfur-rich phosphorus sulfides and alcohols also react to mixtures of α,ω-bis (dialkylthiophosphoryl)sulfanes. But these compounds are not obtained by the reaction of P₄S₁₀ and sulfur with alcohols.     

Über Chalkogenolate. 81. Untersuchungen über N-Hydroxydithiocarbamidsäure 3. Ester der N-Hydroxydithiocarbimidsäure und -carbamidsäure

On Chalcogenolates. 81. Studies on N-Hydroxy Dithiocarbamic Acid. 3- Esters of N-Hydroxy Dithiocarbimic Acid and Dithiocarbamic Acid The reaction between hydroxylamine, carbon disulfide, and alkyl halide leads to the corresponding ester of N-hydroxy dithiocarbimic acid HO? N?C(SR)₂ with R = CH₃, C₂H₅; R₂ = ? CH₂? CH₂? . The phenyl ester of N-hydroxy dithiocarbamic acid HO? NH? CS(SC₆H₅) has been prepared by reaction of hydroxylammonium chloride with the phenyl ester of chlorodithioformic acid. N-Methyl hydroxylammonium chloride reacts with carbon disulfide and alkyl iodide to form the corresponding ester of the dithiocarbamic acid HO? N(CH₃)? CS(SR) with R = CH₃, C₂H₅. The unstable compounds have been characterized by different methods.