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. 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, 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. 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. 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. 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. 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. 141. Untersuchungen über Trimethylsilylxanthogensäure. 1. Darstellung und Eigenschaften von Trimethylsilylxanthaten

On Chalcogenolates. 141. Studies on Trimethylsilyl Xanthic Acid. 1. Synthesis and Properties of Trimethylsilyl Xanthates The trimethylsilyl xanthates have been prepared by reaction of the corresponding silanolate with carbon disulfide. The compounds were characterized by means of chemical and diverse spectroscopic methods. The existence of unstable trimethylsilyl xanthic acid has been demonstrated.     

Über Chalkogenolate. 105. Untersuchungen über Guanidinodithioformiate. 1. Darstellung und Eigenschaften von Guanidinodithioameisensäure

On Chalcogenolates. 105. Studies on Guanidinodithioformates. 1. Synthesis and Properties of Guanidinodithioformic Acid Yellow guanidinodithioformic acid has been prepared by reaction of guanidinium guanidinodithioformate in aqueous solution with concentrated hydrochloric acid at 0°C and characterized by diverse methods.     

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. 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. LIII. Untersuchungen über Thioameisensäuren 1. Darstellung und Eigenschaften von Monothioformiaten und Monothioameisensäure

Na[HCOS] or [KHCOS] were prepared by hydrolysis of phenyl formate with NaHS or KHS. The monomeric monothioformic acid is formed on treatment of Na[HCOS] with 18% HCl and it can be distilled from the solution in a vakuum at ?5°C. The pale yellowish acid exists in the thiol form HCOSH and polymerizes even at 30°C. The S-methyl ester HCO(SCH₃) is formed on reaction of Na[HCOS] with methyl iodide, and the O-methyl ester HCS(OCH₃) on reaction of methyl orthoformate and H₂S in the presence of ZnCl₂ and hydroquinone. The prepared compounds were characterised by different methods.     

Über Chalkogenolate. LVII. Untersuchungen über Thioameisensäuren 5. Darstellung und Eigenschaften von Estern der Dithioameisensäure

Esters of the trimeric dithioformic acid [HCS(SR)]₃ were prepared by interaction of K[HCS₂] with alkyl iodides (R = CH₃, C₂H₅). Orthoesters HC(SR)₃ and di-orthoesters of the monomeric dithioformic acid were formed by reaction of formic acid with thioles (RSH mit R = CH₃, C₂H₅, CH₂C₆H₅) or dithioles (HS? (CH₂)_n? SH with n = 2, 3,4). The prepared compound were characterised by different methods.     

Über Chalkogenolate. LXI. Untersuchungen über Halbester der Kohlensäure. 1. Darstellung und Eigenschaften von Monomethyl- und Monoäthylcarbonaten

On Chalcogenolates. LXI. Studies on Hemiesters of Carbonic Acid. 1. Preparation and Properties of Monomethyl and Monoethyl Carbonates Monoalkyl carbonates M[O₂COR] with M = Li, Na, K, Rb, Cs, Tl, and R = CH₃, C₂H₅ were formed by reaction of CO₂ with alcoholates. The prepared compounds are investigated by different methods.     

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. 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. 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. 144. Darstellung und Eigenschaften von Alkalimetall-t-butyl-carbonaten,Neue Untersuchungen über Trimethylsilylcarbonate

On Chalcogenolates. 144. Synthesis and Properties of Alkali Metal t-Butyl Carbonates. Reinvestigations of Trimethylsilyl Carbonates The t-butyl carbonates M[O₂C? OC(CH₃)₃], where M = Li, Na, K, Rb, Cs, have been prepared by reaction of the corresponding t-butoxide with CO₂ and characterized by means of diverse methods. The equivalent conductivities of the [O₂C? OC(CH₃)₃]^? ion in aqueous solution have been determined and the Stokes radius, the radius of the hydrated ion, and the diffusion coefficient were calculated. The dissociation constant of t-butyl carbonic acid in water at 25°C is K_a = (1.63 ± 0.03)· 10^?8. The thermodynamic data of dissociation were calculated. New data of trimethylsilyl carbonates [O₂C? OSi(CH₃)₃]^? are given.