Über Chalkogenolate. 203. Derivate der Selendithioallophansäure 2. Darstellung und Eigenschaften von Alkylestern

On Chalcogenolates. 203. Derivatives of Selenodithioallophanic Acid. 2. Preparation and Properties of Alkyl Esters Synthesis and properties of selenodithioallophanic acid esters H₂N? CSe? NH? CS? SR where R = CH₃, C₂H₅ as well as their characterization by means of electron absorption, infrared, and nuclear magnetic resonance spectra are described.     

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. 205. Reaktion von Acetamid mit Kohlenstoffdisulfid 2. Ester der N-Acetyldithiocarbamidsäure

On Chalcogenolates. 205. Reaction of Acetamide with Carbon Disulfide. 2. Esters of N-Acetyl Dithiocarbamic Acid The prepared yellow esters of N-acetyl dithiocarbamic acid H₃C? CO? NH? CS? SR with R = CH₃, C₂H₅ have been characterized by means of mass, electron absorption, infrared, and nuclear magnetic resonance spectra.     

Über Chalkogenolate. 204. Reaktion von Acetamid mit Kohlenstoffdisulfid. 1. Darstellung und Eigenschaften von N-Acetyldithiocarbamaten

On Chalcogenolates. 204. Reaction of Acetamide with Carbon Disulfide. 1. Synthesis and Properties of N-Acetyl Dithiocarbamates Acetamide reacts with carbon disulfide in the presence of a strong base to form via the tetrabutyl ammonium salt the N-acetyl dithiocarbamates M[S₂C? NH? CO? CH₃] with M = Na, K, Rb, Cs, [N(ⁿC₄H₉)₄]. The new compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Attempts to synthesize N-acetyl dithiocarbamic acid were not successful.     

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. 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. 175. Reaktion von Acetamidin mit Kohlenstoffdisulfid 4. Darstellung und Charakterisierung der N-Acetimidoyldithiocarbamidsäure

On Chalcogenolates. 175. Reaction of Acetamidine with Carbon Disulfide. 4. Synthesis and Characterization of N-Acetimidoyl Dithiocarbamic Acid Orange colored N-acetimidoyl dithiocarbamic acid has been prepared by reaction of the acetimidinium salt in aqueous solution with hydrochloric acid at 0°C. The properties and the thermal behaviour of the acid have been described, its decomposition in solution has been studied at 20°C kinetically.     

Über Chalkogenolate. 136 [1]. Alkylester der Cyanoameisensäure und der Cyanomonothioameisensäure

On Chalcogenolates. 136. Alkyl Esters of Cyanoformic Acid and of Cyanomonothioformic Acid By use of the phase transfer catalyst 18-crown-6 the esters CH₃O—CO—CN, C₂H₅O—CO—CN, C₂H₅S—CO—CN, and ⁿC₃H₇S—CO—CN have been prepared by reaction of the corresponding chloro compound with potassium cyanide. The prepared compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Über Chalkogenolate. 152. Untersuchungen über Derivate der N-Thioformyldithiocarbamidsäure. 2. Kristallstruktur von Tetra-n-butylammonium-N-thioformyldithiocarbamat

On Chalcogenolates. 152. Studies on Derivatives of N-Thioformyl Dithiocarbamic Acid. 2. Crystal Structure of Tetra-n-butylammonium N-Thioformyl Dithiocarbamate The title compound [N(ⁿC₄H₉)₄][S₂C? NH? CS? H] crystallizes with Z = 2 in the triclinic space group P1 with cell dimensions a = 9.694(2) Å, b = 11.478(3) Å, c = 12.551(6) Å, α = 63.03(3)°, β = 66.42(2)°, γ = 85.60(2)°. The crystal structure has been determined from single crystal X-ray data measured at 20°C and refined to a conventional R of 0.061 for 2249 independent reflections (R_w = 0.042). The structure is built up of dimeric aggregates consisting of 2[N(ⁿC₄H₉)₄]⁺ cations and 2[S₂C? NH? CS? H]^? anions. The two anions are linked together by ? CS? S…?H? N bridges. To make possible a space saving stacking of the dimeric aggregates in the crystal, one methyl group in terminal position of one n-butyl chain in the cation has gauche conformation.     

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.     

Derivate von Tricyanmethan. 2. Untersuchungen über Methyltricyanmethan (1,1,1-Tricyanethan) [1]

Derivatives of Tricyanomethane. 2. Studies on Methyl Tricyanomethane (1,1,1-Tricyanoethane) The title compound H₃C? C(CN)₃ has been characterized by means of nuclear magnetic resonance, vibrational, and mass spectra.     

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, 83 Untersuchungen über Halbester der Trithiokohlensäure 1. Darstellung und Eigenschaften von Thioxanthaten

On Chalcogenolates. 83. Studies on Hemiesters of Trithocarbonic ACld. 1. Preparation and Properties of Thoxanthates Thioxanthates of alkli metals K[S₂C? SR] · H₂O with R = CH₃, C₂H₅, ⁿC₃H₇, ⁱC₃H₇, ^sC₄H₉, ^tC₄H₉ M[S₂C? S-ⁿC₄H₉] · H₂O with M = Na, K, Rb, Cs have been prepared by reaction of alkanethiols with OS₂ and the corresponding hydroxide. The i.r. spectra, electron absorption spectra, and ¹H-n.m.r. spectra have been assigned.     

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. 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. 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. 101. Untersuchungen über Halbester der Monothiokohlensäure. 1. Darstellung und Eigenschaften von Oxoxanthaten

On Chalcogenolates. 101. Studies on Hemiesters of Monothiocarbonic Acid. 1. Preparation and Properties of Oxoxanthates Alkyl oxoxanthates of alkali metals have been prepared by reaction of COS with the corresponding alkoxides. The reaction of ethyl oxoxanthate with methyl iodide leads to S-methyl-O-ethyl ester of monothiocarbonic acid. The oxidation of [SOC? OC₂H₅]^? ions with iodine forms bis(ethoxycarbonyl)-disulfide (S? CO? OC₂H₅)₂. The prepared compounds have been characterized with chemical and thermoanalytical methods as well as by means of electron absorption spectra, infrared spectra, ¹H-NMR spectra, and mass spectra.     

Über Chalkogenolate. 121. Untersuchungen über N-Cyanomonothiocarbimidsäure 1. Darstellung und Eigenschaften von Alkalimetall-N-cyanomonothiocarbimaten

On Chalcogenolates. 121. Studies on N-Cyanomonothiocarbimic Acid. 1. Synthesis and Properties of Alkali Metal N-Cyanomonothiocarbimates The hitherto unknown N-cyanomonothiocarbimates M₂[SOC?N? CN] · H₂O, where M = Na, K, Rb, Cs, have been prepared by reaction of the corresponding alkali metal salt of cyanamide with COS. N-Cyanomonothiocarbimates react with sulfur to form the ion, which gives with an acid and with CH₃I the methyl compound . The reaction of the latter compound with H₂O₂ yields . All compounds have been characterized by means of diverse 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. 132. Untersuchungen über Rhodanine 3. Darstellung und Charakterisierung von Thiorhodanin und 5-Methylthiorhodanin. Versuche zur Herstellung von Trithiopyruvinsäure

On Chalcogenolates. 132. Studies on Rhodanines. 3. Synthesis and Characterization of Thiorhodanine and 5-Methyl Thiorhodanine. Attempts to Prepare Trithiopyruvic Acid The reactions of rhodanine and 5-methyl rhodanine with P₄S₁₀ and with Lawesson reagent yield the title compounds, which have been characterized with electron absorption, ¹H and ¹³C NMR, infrared, and mass spectra. Attempts to synthesize trithiopyruvic acid by use of different procedures were not successful.