Über Chalkogenolate. 153. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure 3. Ester der N-Thioformyldithiocarbamidsäure und Oxydation von N-Thioformyldithiocarbamaten

On Chalcogenolates. 153. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 3. Esters of N-Thioformyl Dithiocarbamic Acid and Oxidation of N-Thioformyl Dithiocarbamates The esters of N-thioformyl dithiocarbamic acid have been prepared by reaction of tetra-n-butylammonium N-thioformyl dithiocarbamate with the corresponding alkyl iodide. Also the reaction of S-methyl N-formyl dithiocarbamate with Lawesson reagent forms the methyl ester of N-thioformyl dithiocarbamic acid. The oxidation of N-thioformyl dithiocarbamates with iodine yields 1,2,4-dithiazole-3-thione All compounds have been characterized by means of chemical and diverse spectroscopic methods. A new method to prepare 5-phenyl 1,2,4-dithiazole-3-thione is given.     

Über Chalkogenolate. 94. Untersuchungen über Trithioallophansäure 3. Ester der Trithioallophansäure [1]

On Chalcogenolates. 94. Studies on Trithioallophanic Acid. 3. Esters of Trithioallophanic Acid. The esters of trithioallophanic acid H₂N? CS? NH? CS(SR) with R = CH₃, CH₂C₆H₅ have been characterized by means of electron absorption spectra, infrared spectra, ¹H NMR spectra, and mass spectra.     

Über Chalkogenolate. 79. Untersuchungen über N-Hydroxydithiocarbamidsäure 1. Darstellung und Eigenschaften von N-Hydroxydithiocarbamaten und von Hydroxylammoniumdithiocarbamat

On Chalcogenolates. 79. Studies on N-Hydroxy Dithiocarbamic Acid. 1. Preparation and Properties of N-Hydroxy Dithiocarbamates and of Hydroxylammonium Dithiocarbamate In the presence of the corresponding hydroxide the reactions between hydroxylamine and carbon disulfide lead to N-hydroxy dithiocarbamates and [H₃NOH][S₂C? NH₂], respectively. The unstable compounds have been characterized by different methods.     

Über Chalkogenolate. 89. Untersuchungen über N-Dicyandithiocarbamidsäure Darstellung und Eigenschaften der freien Säure

On Chalcogenolates. 89. Studies on N-Dicyandithiocarbamic Acid. Preparation and Properties of the Free Acid Colorless N-dicyandithiocarbamic acid (melting point: 112°C) has been prepared by reaction between a suspension of K[S₂C? N(CN)₂] in diethyl ether and a solution of HCl in (C₂H₅)₂O at 0°C; the ether was distilled off at 0°C in vacuo. The compound has been characterized by means of infared spectra, electron absorption spectra, ¹H-NMR spectra, and mass spectra. The dissociation constant of N-dicyandithiocarbamic acid in water is K_a = (1.69 ± 0.1) X 10^?1 20°C. The thermodynamic data of the dissociation were calculated.     

Über Chalkogenolate. 109. Untersuchungen über Perthiocyansäure 2. Darstellung und Eigenschaften der freien Säure

On Chalcogenolates. 109. Studies on Perthiocyanic Acid. 2. Preparation and Properties of the Free Acid Pale yellow perthiocyanic acid has been prepared by reaction of an aqueous solution of barium perthiocyanate with dilute hydrochloric acid at 0°C in the presence of diethyl ether. The infrared, electron absorption, and mass spectra are communicated.     

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. LV. Untersuchungen über Thioameisensäuren. 3. Darstellung und Eigenschaften der Dithioameisensäure

Amorphous trimeric dithioformic acid has been prepared by interaction between an aqueous solution of K[HCS₂] and HCl(aq). After 1/2 – 1 minutes, the polymeric acid [ HCS(SH)]_X precipitates from a clear yellow solution of [HCS(SH)]₃ in N,N-dimethyl formamide or dimethyl sulfoxide. In solution (HCCl₃, H₂CCl₂), the existence of monomeric dithioformic acid has been verified. In the gaseous state [HCS(SH)]_n exists with n = 1, 2, 3. The dithioformic acid was investigated by different methods.     

Über Chalkogenolate. LVIII. Untersuchungen über Thiomeiensäuren 6. Cyandithioameisensäure und Azidodithioameisensäure

Polymeric cyanodithioformic acid has been prepared by interaction between a solution of Na[NCCS₂]. 3 DMF and HCl(aq). In the gaseous state there exists [NCCS(SH)]_x with x = 1 and 2. The instable crystalline acidodithioformic acid is formed on reaction of Na[N₃CS₂] with HCl(aq). In the gaseous state there exists the monomeric acid N₃CS(SH).     

Über Chalkogenolate. 82 [1]. N-Hydroxycarbamate und Ester der N-Hydroxycarbamidsäure und -carbimidsäure

On Chalcogenolates. 82. N-Hydroxy Carbamates and Esters of N-Hydroxy Carbamic Acid and Carbamic Acid The reaction between hydroxylammonium chloride, CO₂, and the corresponding hydroxide leads to N-hydroxy carbamates Esters of N-hydroxy carbamic acid have been prepared by reaction of N-hydroxy carbamates with alkyl bromide. – At room temperature the ethyl ester decomposes and forms the ester of N-hydroxy carbimic acid HO? N?C(OC₂H₅)₂. The prepared compounds have been characterized by different methods.     

Über Chalkogenolate. 151. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure. 1. Darstellung und Eigenschaften von N-Thioformyldithiocarbamaten

On Chalcogenolates. 151. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 1. Synthesis and Properties of N-Thioformyl Dithiocarbamates The N-thioformyl dithiocarbamates M[S₂C? NH? CS? H], where M = K, Rb, Cs, Tl, NH₄, [N(ⁿC₄H₉)₄], Na[S₂C? NH? CS? H] · 0.5 H₂O, and Ba[S₂C? NH? CS? H]₂ · 3 HO? CH₂? CH₂? OCH₃ have been prepared by use of partial different procedures. The compounds were characterized with chemical and thermal methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Attempts to synthesize N-thioformyl dithiocarbamic acid were not successful.     

Über Chalkogenolate. 206 [1]. N-Thioacetyldithiocarbamate und Ester der N-Thioacetyldithiocarbamidsäure

On Chalcogenolates. 206. N-Thioacetyl Dithiocarbamates and Esters of N-Thioacetyl Dithiocarbamic Acid Thioacetamide reacts with carbon disulfide in the presence of KH to form via the tetrabutyl ammonium salt dark yellow N-thioacetyl dithiocarbamates M[S₂C? NH? CS? CH₃], where M = K, Rb, Cs. The salts as well as the methyl and ethyl ester have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Attempts to synthesize N-thioacetyl dithiocarbamic acid were not successful.     

Über Chalkogenolate. 129. Untersuchungen über Ester der N-Cyancarbamidsäure. 2. Darstellung,spektroskopische Charakterisierung und Zersetzung von O-Methyl- und O-Ethyl-N-cyancarbamat

On Chalcogenolates. 129. Studies on Esters of N-Cyancarbamic Acid. 2. Synthesis, Spectroscopic Characterization, and Decomposition of O-Methyl and O-Ethyl N-Cyancarbamate NH₄[NC? N? CO? OR], where R = CH₃ and C₂H₅, reacts with acids to yield unstable NC? NH? CO? OR. The esters decompose to form NC? N?C(NH₂)? NH? CO? OR. The compounds have been characterized by means of electron absorption, ¹H and ¹³C NMR, infrared, and mass spectra.     

Über Chalkogenolate. 108. Untersuchungen über Perthiocyansäure 1. Darstellung und Eigenschaften von Perthiocyanaten

On Chalcogenolates. 108. Studies on Perthiocyanic Acid. 1. Synthesis and Properties of Perthiocyanates The perthiocyanates have been prepared by different techniques. The compounds were characterized by means of diverse methods.     

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. 142. Untersuchungen über Trimethylsilylxanthogensäure. 2. S-Methyl- und S-Ethyltrimethylsilylxanthat

On Chalcogenolates. 142. Studies on Trimethylsilyl Xanthic Acid. 2. S-Methyl and S-Ethyl Trimethylsilyl Xanthates The hitherto unknown S-alkyl trimethylsilyl xanthates (CH₃)₃SiO? CS? SR, where R = CH₃ and C₂H₅, have been characterized with electron absorption, infrared, nuclear magnetic resonance (¹H, ¹³C, and ²⁹Si), and mass spectra.     

Über Chalkogenolate. 104. Untersuchungen über Halbester der Monothiokohlensäure. 3. Kristallstruktur von Kaliummethyloxoxanthat

On Chalcogenolates. 104. Studies on Hemiesters of Monothiocarbonic Acid. 3. Crystal Structure of Potassium Methyl Oxoxanthate K[SOC? OCH₃] crystallizes with Z = 4 in the monoclinic space group P2₁/n with cell dimensions a = 6.742(5), b = 6.968(5), c = 10.777(6) Å, β = 104.6(6)°. The structure has been determined from single crystal X-ray data by means of Patterson and Fourier synthesis and refined to a final conventional R value of 0.037 using 1292 independent reflexions. The structure is built up of K⁺ and [SOC? OCH₃]^? ions. The potassium ion is bonded to four oxygen and four sulfur atoms from five oxoxanthate ions. The coordination polyhedron consists of two reciprocally penetrated and distorted O₄ and S₄ tetrahedra.     

Über Chalkogenolate. 134. Untersuchungen über Ester von Halogenoameisensäuren 2. Darstellung und Eigenschaften von Se-Alkylestern der Chloromonothiomonoselenoameisensäure [1]

On Chalcogenolates. 134. Studies on Esters of Haloformic Acids 2. Synthesis and Properties of Se-Alkyl Esters of Chloromonothiomonoselenoformic Acid The hitherto unknown esters RSe? CS? Cl with R ? C₂H₅ and ⁿC₃H₇ have been prepared by reaction of thiophosgene with the corresponding alkane selenol. The compounds have been characterized with electron absorption, nuclear magnetic resonance (¹H, ¹³C, and ⁷⁷Se), infrared, and mass spectra.     

Über Chalkogenolate. 99. Untersuchungen über Monothiocarbamidsäure 1. Darstellung und Eigenschaften von Monothiocarbamaten

On Chalcogenolates. 99. Studies on Monothiocarbamic Acid. 1. Synthesis and Properties of Monothiocarbamates The monothiocarbamates , and Ba[SOC? NH₂]₂ have been prepared and characterized by means of infrared, electron absorption, and mass spectra. The existence of the free monothiocarbamic acid was ascertained.     

Über Chalkogenolate. 92. Untersuchungen über Trithioallophansäure 1. Alkalimetalltrithioallophanate

On Chalcogenolates. 92. Studies on Trithioallophanic Acid 1. Trithioallophanates of Alkali Metals The trithioallophanates have been prepared by reaction of H₂S with the corresponding dithiocarbimate. The compounds have been characterized by different methods. In aqueous solution the equivalent conductivites of [S₂C? NH? CS? NH₂]^? have been determined by means of conductivity measurements. The Stokes radius of the ion, the radius of the hydrated ion, and its diffusion coefficient were calculated.     

Über Chalkogenolate. 128. Untersuchungen über Ester der N-Cyancarbamidsäure. 1. Darstellung und Eigenschaften der Ammoniumsalze von N-Cyancarbamidsäureestern und vom N-Methyl-N-cyancarbamidsäureethylester

On Chalcogenolates. 128. Studies on Esters of N-Cyancarbamic Acid. 1. Synthesis and Properties of Ammonium Salts of N-Cyancarbamic Acid Esters and of the Ethyl Ester of N-Methyl N-Cyancarbamic Acid The reaction of NC? N(CO? OR)₂ with NH₃(g) yields NH₄[NC? N? CO? OR], where R = CH₃, C₂H₅, and C₆H₅. NH₄[NC? N? CO? OC₂H₅] reacts with H₃CI to form NC? N(CH₃)? CO? OC₂H₅. The called compounds have been studied with chemical and spectroscopic methods.