Über Chalkogenolate. 93. Untersuchungen über Trithioallophansäure 2. Darstellung und Eigenschaften der freien Säure [1]

On Chalcogenolates. 93. Studies on Trithioallophanic Acid 2. Preparation and Properties of the Free Acid Yellow trithioallophanic acid H₂N? CS? NH? CS(SH) has been prepared by reaction between a suspension of K[S₂C? NH? CS? NH₂] in diethyl ether and a solution of HCl in (C₂H₅)₂O at ?15°C; the ether was distilled off at ?15°C in vacuo. The compound has been characterized by means of infrared spectra, electron absorption, ¹H-NMR spectra, and mass spectra. The dissociation constant of trithioallophanic acid in water is K_a = (1,41 ± 0,08) · 10^?2 at 20°C.     

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. 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. 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. 149. Reaktion von Formamid mit Kohlenstoffdisulfid 3. N-Formyldithiocarbamidsäure H?CO?NH?CS?SH

On Chalcogenolates. 149. Reaction of Formamide with Carbon Disulfide. 3. N-Formyl Dithiocarbamic Acid H? CO? NH? CS? SH The reaction of a suspension of K[S₂C? NH? CO? H] in diethyl ether with a solution of HCl(g) in ether at ?15°C forms H? CO? NH? CS? SH. The acid has been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra.     

Über Chalkogenolate. 165. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 4. Salze des S-Methylesters der N-Dithiomethylendithiocarbazidsäure

On Chalcogenolates. 165. Reactions of Hydrazine with Carbon Disulfide. 4. Salts of the S-Methyl Ester of N-Dithiomethylene-dithiocarbazic Acid The S-methyl ester of dithiocarbazic acid reacts with carbon disulfide in the presence of sodium or potassium hydride at ?15°C to yield the hitherto unknown salts of the S-methyl ester of N-dithiomethylene-dithiocarbazic acid. The prepared compounds , have been studied with chemical methods as well as with electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Über Chalkogenolate. 96 [1]. Untersuchungen über Alkalimetalltrimethylsilylcarbonate

On Chalcogenolates. 96. Studies on Trimethylsilyl Carbonates of Alkali Metals The trimethylsilyl carbonates M[O₂COSi(CH₃)₃] with M = Li, Na, K, Rb, Cs have been prepared by reaction of Co₂ with the corresponding silanolate. Infrared spectra, electron absorption spectra, ¹H-NMR spectra as well as mass spectra are communicated. In aqueous solution the equivalent conductivities of [O₂COSi(CH₃)₃]^? have been determined by means of conductivity measurements. The diffusion coefficient of the ion was calculated. The dissociation constant of trimethylsilyl carbonic acid in water at 20°C is K_a = (4,83 ± 0,5) · 10^?10. The thermodynamic data of the dissociation were calculated.     

Über Chalkogenolate. 155. Reaktion von N-Methylformamid mit Kohlenstoffdisulfid 2. N-Methyl-N-formyldithiocarbamidsäure und Oxydation von N-Methyl-N-formyldithiocarbamaten

On Chalcogenolates. 155. Reaction of N-Methyl Formamide with Carbon Disulfide. 2. N-Methyl N-Formyl Dithiocarbamic Acid and Oxidation of N-Methyl N-Formyl Dithiocarbamates The reaction of a solution of K[S₂C? NCH₃? CO? H] in acetone-d₆ with gaseous HCl at ?78°C forms unstable H? CO? NCH₃? CS? SH. The existence of this acid in solution has been demonstrated by nuclear magnetic resonance spectra. The oxidation of N-methyl N-formyl dithiocarbamates with iodine yields N,N′-dimethyl N,N′-diformyl thiuram disulfide (H? CO? NCH₃? CS? S? )₂, which has been characterized by means of diverse spectroscopic methods.     

Über Chalkogenolate. 117 [1]. Untersuchungen über Guanidinodithioformiate 4. Kristall- und Molekülstruktur der Guanidinodithioameisensäure

On Chalcogenolates. 117. Studies on Guanidinodithioformates. 4. Crystal and Molecular Structure of Guanidinodithioformic Acid Guanidinodithioformic acid crystallizes with Z = 4 in the monoclinic space group P2₁ with cell dimensions a = 4.204(3) Å, b = 10.422(5) Å, c = 12.491(5) Å, β = 93.9(3)°. The crystal and molecular structure has been determined from single crystal X-ray data at 20°C and refined to a conventional R of 0.0242. The asymmetric part of the unit cell contains two molecules in the dipolar form with different conformation. The molecules have delocated double-bonds and are linked together by N? H···S hydrogen bridges.     

Über Chalkogenolate. 111. Untersuchungen über Perthiocyansäure. 4. Kristall- und Molekülstruktur von Dimethylperthiocyanat

On Chalcogenolates. 111. Studies on Perthiocyanic Acid. 4. Crystal and Molecular Structure of Dimethyl Perthiocyanate (CH₃)₂C₂N₂S₃ crystallizes with Z = 4 in the monoclinic space group P2₁/c with cell dimensions a = 7.661(4) Å, b = 11.675(5) Å, c = 9.549(5) Å, β = 116.7(3)·. The crystal and molecular structure has been determined from single X-ray data at 20°C and refined to a conventional R of 0.062. The structure consists of isolated 3,5-bis(methylmercapto)-1,2,4-thiadiazole molecules. The 1,2,4-thiadiazole ring is plane and stabilized by mesomerism.     

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.     

Über Chalkogenolate. 160. Umsetzung von 1,2-Ethandithiolaten mit Kohlenstoffdisulfid 2. 1,2-Ethan-bis(trithiokohlensäure) und Alkylester der Säure

On Chalcogenolates. 160. Reaction of 1,2-Ethanedithiolates with Carbon Disulfide. 2. 1,2-Ethane-bis(trithiocarbonic acid) and Alkyl Esters of This Acid The reaction of potassium 1,2-ethane-bis(trithiocarbonate) with hydrochloric acid at 0°C gives unstable, deep yellow coloured 1,2-ethane-bis(trithiocarbonic acid) The 1,2-ethane-bis(alkyl trithiocarbonates) RS? CS? SCH₂CH₂S? CS? SR, where R = CH₃ and C₂H₅, have been formed by reaction of potassium 1,2-ethane-bis(trithiocarbonate) with the corresponding alkyl iodide. The called compounds have been characterized by means of diverse spectroscopic 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. 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. 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. 191. Ester der 2-Oxophenyldithioessigsäure 2. Kristall- und Molekülstruktur des Methylesters

On Chalcogenolates. 191. Esters of 2-Oxophenyldithioacetic Acid. 2. Crystal and Molecular Structure of the Methyl Ester The title compound C₆H₅? CO? CS? SCH₃ crystallizes with Z = 2 in the triclinic space group P1 with cell dimensions (?60°C) a = 6.236(4) Å, b = 7.972(2) Å, c = 9.589(4) Å, α = 88.42(3)°, β = 75.39(5)°, γ = 81.54(4)°. The structure has been determined from single crystal X-ray data measured at ?60°C and refined to R = 0.085 and R_w = 0.087 for 2307 independent reflections. With nearly 20° the C?O bond is turned out of the plane of the phenyl ring.     

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. 102. Untersuchungen über Halbester der Monothiokohlensäure. 2. Kristallstruktur von Rubidiummethyloxoxanthat

On Chalcogenolates. 102. Studies on Hemiesters of Monothiocarbonic Acid. 2. Crystal Structure of Rubidium Methyl Oxoxanthate Rb[SOC? OCH₃] crystallizes with Z = 4 in the monoclinic space group P2₁/c with cell dimensions a = 4.332(3) Å, b = 11.349(5) Å, c = 10.673(5) Å, β = 92.9(5)°. The structure has been determined from single crystal X-ray data by means of Patterson and Fourier syntheses and refined to a final conventional R value of 0.045 using 983 independent reflexions. The structure consists of Rb⁺ and [SOC? OCH₃]^? ions. The rubidium ion is bonded to five oxygen and three sulfur atoms. The coordination polyhedron is a bicapped trigonal prism.     

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. 156. Reaktion von N-Methylformamid mit Kohlenstoffdisulfid 3. Alkylester der N-Methyl-N-formyldithiocarbamidsäure

On Chalcogenolates. 156. Reaction of N-Methyl Formamide with Carbon Disulfide. 3. Alkyl Esters of N-Methyl N-Formyl Dithiocarbamic Acid The hitherto unknown esters of N-methyl N-formyl dithiocarbamic acid H? CO? NCH₃? CS? SR, where R = CH₃ and C₂H₅, have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.