Über Chalkogenolate. 161. Umsetzung von 1,2-Ethandithiolaten mit Kohlenstoffdisulfid 3. Kristall- und MolekülStruktur von 1,2-Ethan-bis(methyltrithiocarbonat)

On Chalcogenolates. 161. Reaction of 1,2-Ethanedithiolates with Carbon Disulfides. 3. Crystal and Molecular Structure of 1,2-Ethane-bis(methyltrithiocarbonate) The title compound H₃CS? CS? SCH₂CH₂S? CS? SCH₃ crystallizes with Z = 2 in the triclinic space group P1 with cell dimensions a = 6.769(1) Å, b = 8,334(2) Å, c = 11.222(1) Å, α = 80.93(1)°, β = 72.01(1)°, γ = 78.58(2)°. The crystal structure has been determined from single crystal X-ray data measured at ?40°C and refined to a conventional R of 0.035 for 2004 independent reflections (R_w = 0.042). The structure consists of isolated molecules, which are linked together by weak interaction forces. The S? CS? S groups are plane.     

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. Reaktion von Formamid mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von N-Formyl-dithiocarbamaten

On Chalcogenolates. 147. Reaction of Formamide with Carbon Disulfide. 1. Synthesis and Properties of N-Formyl Dithiocarbamates Formamide reacts with carbon disulfide in the presence of sodium hydride to yield crude sodium N-formyl dithiocarbamate. Pure compounds have been produced via N-formyl dithiocarbamic acid. The N-formyl dithiocarbamates were characterized by means of diverse methods.     

Über Chalkogenolate. 162. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 1. Darstellung und Eigenschaften von 1,2-Hydrazin-bis(dithioformiaten)

On Chalcogenolates. 162. Reactions of Hydrazine with Carbon Disulfide. 1. Synthesis and Properties of 1,2-Hydrazine-bis (dithioformates) The prepared 1,2-hydrazine-bis(dithioformates) have been characterized with chemical methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Über Chalkogenolate. 154. Reaktion von N-Methylformamid mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von N-Methyl-N-formyl-dithiocarbamaten

On Chalcogenolates. 154. Reaction of N-Methyl Formamide with Carbon Disulfide. 1. Synthesis and Properties of N-Methyl N-Formyl Dithiocarbamates N-Methyl formamide reacts with carbon disulfide in the presence of sodium hydride, potassium hydroxide, and barium hydroxide to form the corresponding N-methyl N-formyl dithiocarbamate. The prepared compounds have been characterized with chemical and thermal methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Über Chalkogenolate. 172. Reaktion von Acetamidin mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von N-Acetimidoyldithiocarbamaten

On Chalcogenolates. 172. Reaction of Acetamidine with Carbon Disulfide. 1. Synthesis and Properties of N-Acetimidoyl Dithiocarbamates The reaction of acetamidine H₂N? C(CH₃)?NH with CS₂ at ?15°C yields the acetamidinium salt of N-acetimidoyl dithiocarbamic acid. It reacts with hydroxides to form the corresponding N-acetimidoyl dithiocarbamates. The properties and the thermal behaviour of the prepared compounds \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm M}[{\rm S}_2 {\rm C} - {\rm N} = {\rm C}({\rm CH}_{\rm 3} ) - {\rm NH}_2 ]{\rm with M} = [({\rm H}_2 {\rm N})_2 {\rm C} - {\rm CH}_3 ],{\rm Na} \cdot {\rm CH}_3 {\rm OH},{\rm K} \cdot {\rm H}_2 {\rm O},{\rm Rb},{\rm Cs},{\rm Tl},{\rm Pb}/2{\rm and Cd}/2 \cdot {\rm H}_2 {\rm O} $\end{document} have been described. The decomposition in solution has been studied at 20°C kinetically.     

Über Chalkogenolate. 157. Reaktion von N-Methylthioformamid mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von N-Methyl-N-thioformyldithiocarbamaten

On Chalcogenolates. 157. Reaction of N-Methyl Thioformamide with Carbon Disulfide. 1. Synthesis and Properties of N-Methyl N-Thioformyl Dithiocarbamates N-Methyl thioformamide has been prepared by reaction of N-methyl formamide with P₄S₁₀. It reacts with carbon disulfide in the presence of hydroxides to yield the corresponding N-methyl N-thioformyl dithiocarbamate. The prepared compounds have been characterized with chemical and thermoanalytical methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Attempts to synthesize N-methyl N-thioformyl dithiocarbamic acid were not successful.     

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. 113 Umsetzung von Chloramin mit Kohlenstoffdisulfid und mit Methylestern von Dithiocarbamidsäuren

On Chalcogenolates. 113. Reactions of Chloramine with Carbon Disulfide and with Methylesters of Dithiocarbamic Acids The reactions of chloramine with CS₂ and with H₂N? CS? SCH₃, CH₃? NH? CS? SCH₃, and (CH₃)₂N? CS? SCH₃ have been studied. The reaction with the methylester of dithiocarbamic acid gives the known dimethyl perthiocyanate and the reaction with the methylester of N-methyldithiocarbamic acid leads to CH₃S? CS? N(CH₃)? C(?NCH₃)? SCH₃. The latter compound has been characterized by means of electron absorption spectra, infrared spectra, nuclear magnetic resonance spectra (¹H and ¹³C), and mass spectra.     

Über Chalkogenolate. 120. Darstellung und Eigenschaften von N-Cyanguanidinomonothioformiaten

On Chalcogenolates. 120. Synthesis and Properties of N-Cyanguanidino Monothioformates N-Cyanguanidine reacts with COS in the presence of the corresponding alkali metal hydroxide to form N-cyanguanidino monothioformates M[SOC? NH? C(NH₂)?N? CN]. The compounds with M = K, Rb, Cs and the methyl ester have been characterized by means of electron absorption, ¹H and ¹³C NMR, infrared, and mass spectra.     

Über Chalkogenolate. 103. Reaktion von Guanidin mit Kohlenstoffdisulfid

On Chalcogenolates. 103. Reaction of Guanidine with Carbon Disulfide The reaction between guanidine and carbon disulfide in cold aqueous acetone leads to guanidinium guanidinodithioformate. In heat the reaction gives guanidinium trithiocarbonate and the guanidinium salt of 4-imino-2,6-dithio-1,3,5-thiadiazine. In ethanolic solution guanidine reacts with carbon disulfide to form guanidinium ethyl xanthate. The prepared compounds have been characterized with chemical methods as well as by means of electron absorption spectra, i.r. spectra, n.m.r. spectra, and mass spectra.     

Über Chalkogenolate. 168. Reaktion von N,N′-Diphenylformamidin mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von N,N′-Diphenyl-N-form-imidoyldithiocarbamaten

On Chalcogenolates. 168. Reaction of N,N′-Diphenyl Formamidine with Carbon Disulfide. 1. Synthesis and Properties of N,N′-Diphenyl N-Formimidoyl Dithiocarbamates N,N′-Diphenyl formamidine H? N(C₆H₅)? CH?NC₆H₅ reacts in different solvents with CS₂ in the presence of an alkali metal hydroxide to produce N,N′-diphenyl N-formimidoyl dithiocarbamate solvates. The properties of the prepared compounds (L = H₂O, acetonitrile, dioxane, dimethoxyethane, acetone, and mixed solvates) and of the Tl, Ba, and Pb salts are described.     

Über Chalkogenolate. 124. Reaktion von Alkalimetallchloriden mit Kohlenstoffdisulfid

On Chalcogenolates. 124. Reaction of Alkali Metal Chlorides with Carbon Disulfide Alkali metal chlorides react with carbon disulfide in acetonitrile in the presence of solid sodium hydroxide as catalyst to form the corresponding yellow instable chlorodithioformates. The compounds M[S₂C? Cl], where M = Na, K, Rb, Cs, have been prepared and characterized by means of chemical and spectroscopic methods.     

Über Chalkogenolate. 164. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 3. Synthese und Charakterisierung von Trinatrium-1,2-hydrazin-bis(dithiocarboxylat)

On Chalcogenolates. 164. Reactions of Hydrazine with Carbon Disulfide. 3. Synthesis and Characterization of Trisodium 1,2-Hydrazine-bis(dithiocarboxylate) The mixed dithiocarbamate-dithiocarbimate Na₃[S₂C? NH? N°CS₂] · 7 H₂O has been prepared by reaction of H₂N? NH₂ · H₂O with CS₂ and NaOH in aqueous solution. It has been characterized by means of diverse methods.     

Über Chalkogenolate. 125. Untersuchungen über N-Cyanformamidinodithiocarbimidsäure 1. Darstellung und Eigenschaften von N-Cyanformamidinodithiocarbimaten,Umsetzung mit Säuren und elementarem Schwefel

On Chalcogenolates. 125. Studies on N-Cyanformamidino Dithiocarbimic Acid. 1. Synthesis and Properties of N-Cyanformamidino Dithiocarbimates, Reaction with Acids and with Elemental Sulfur N-Cyanguanidine reacts with carbon disulfide in the presence of the corresponding alkali metal hydroxide to form N-cyanformamidino dithiocarbimates M₂[S₂C?N? C(NH₂)?N? CN], where M = K and Rb. They react with acids to form and with elemental sulfur to yield . The potassium salt and the methyl compound were isolated. All compounds have been characterized by chemical and spectroscopic methods.     

Über Chalkogenolate. 163. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid. 2. Kristallstruktur von Dikalium-1,2-hydrazin-bis(dithioformiat)

On Chalcogenolates. 163. Reactions of Hydrazine with Carbon Disulfide. 2. Crystal Structure of Dipotassium 1,2-Hydrazine-bis (dithioformate) The title compound K₂[S₂C? NH? NH? CS₂] ( 1 ) crystallizes with Z = 4 in the orthorhombic space group Pbna with cell dimensions a = 6.635(1), b = 10.825(2), c = 12.866(2) Å. The crystal structure has been determined from single crystal X-ray data measured at ?85 °C and refined to a conventional R of 0.034 for 969 independent reflections (R_w = 0.042). The [S₂C? NH? NH? CS₂]^2? ions are linked together by hydrogen bridges N? H…?S. The K⁺ ions are surrounded by seven sulfur atoms in irregular coordination.     

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. 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. 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. 166. Umsetzungen von Hydrazin mit Kohlenstoffdisulfid 5. Versuche zur Darstellung von Estern der 1,2-Hydrazin-bis(dithiocarbonsäuren) [1]

On Chalcogenolates. 166. Reactions of Hydrazine with Carbon Disulfide. 5. Attempts to Prepare Esters of 1,2-Hydrazine-bis(dithiocarboxylic Acids) Possible reactions to synthesize esters of 1,2-hydrazine-bis(dithiocarboxylic acids) are described:

• 1 The reaction of K₂[S₂C? NH? NH? CS₂] with H₃CI preponderantly forms 2,5-dimethylthio-1,3,4-thiadiazole Ia and a small quantity of bis(methylthio)-ketazine II (formula see ?Inhaltsübersicht”?).
• 2 Hydrazine reacts with Cl? CS? SC₂H₅ to give exclusively compound Ib
• 3 The reaction between K₂[S₂C=N? NH? CS? SCH₃] and H₃CI yields 94% compound Ia and 6% compound II
• 4 K₂[S₂C=N? NH? CS? SCH₃] reacts with C₆H₅? CH₂Br to form a mixture containing 25% dibenzyl sulfide, 15% 2,5-dibenzylthio-1,3,4-thiadiazole I e, and 60% 2-methylthio-5-benzylthio-1,3,4-thiadiazole I d

The compounds Ia , Id and II have been characterized by means of diverse spectroscopic methods. The mechanism of the formation of compounds I has been discussed.