Über die Darstellung von Tricyanmethanidometallbromiden und Organometalltricyanmethaniden durch Reaktionen mit Bromtricyanmethan BrC(CN)3

Different reactions of BrC(CN)₃ with metal bromides (MBr₄; M = Sn, Ti, Zr), metal organyles (SnR₄, MR₂ (R = C₂H₅, C₆H₅; M = Zn, Cd), C₆H₅HgBr) and with phosphorus tribromide are reported. These reactions lead to the formation of new compounds of the types MBr₃NCC(CN)₂, R₃MNCC(CN)₂, RMNCC(CN)₂ and PBr₄NCC(CN)₂, respectively. The structures of the new compounds are discussed, using results of infrared spectroscopic measurements. Mostly the pseudohalide group C(CN)₃ is bonded to the metal via the nitrogen of a cyano group. Unsolubility and IR spectra are characterizing the compounds of the types MBr₃NCC(CN)₂ and RMNCC(CN)₂ as coordination polymers. IIb-metal derivatives form pyridine complexes [RMNCC(CN)₂(C₅H₅N)₂].     

Untersuchungen über die Kinetik und den Mechanismus der Bindung von Schwefeldioxid und Stickoxiden durch gasförmiges Ammoniak

Studies on Kinetics and Mechanism of the Reaction of Sulphur Dioxide and Nitrogen Oxides with Gaseous Ammonia It was found that depending on the partial pressure of SO₂, H₂O, and NH₃ different solid products were formed. Formation of the product containing the smallest amount of the substrate of the lowest partial pressure is favoured. The measured stability limits of the solid products confirmed the former thermodynamic calculations. The conditions for effective binding of NO_x with ammonia were established.     

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. 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. 135. Untersuchungen über Ester von Halogenoameisensäuren 3. Darstellung und Charakterisierung von Fluoro- und Bromothioameisensäurealkylestern

On Chalcogenolates. 135. Studies on Esters of Haloformic Acids. 3. Synthesis and Characterization of Alkyl Esters of Fluoro- and Bromothioformic Acid ⁿC₃H₇S? CO? F, C₂H₅S? CS? F, and ⁿC₃H₇S? CS? F have been prepared by reaction of the corresponding chloro compound with KF by use of phase transfer catalysts. The esters RS? CS? Br, where R ? C₂H₅ and ⁿC₃H₇, are formed by reaction between RSH and SCBr₂ in the presence of pyridine. The compounds have been characterized by means of diverse spectroscopic methods.     

Über Chalkogenolate. LIV. Untersuchungen über Thioameisensäuren 2. Darstellung und Eigenschaften von Dithioformiaten

K[HCS₂] was prepared by interaction of chloroform with K₂S. Rb[HCS₂] and Cs[HCS₂] were formed by reaction of trimeric dithioformic acid with alcoholates (X-ray data see ?Inhaltsübersicht”?). The dithioformates T1[HCS₂], In[HCS₂]₃, and M[HCS₂]₂ with M = Pb, Zn, Cd, Hg, and M[HCS₂] with M = [(C₆H₅)₄P], [(C₆H₅)₄As], [(C₂H₅)₄N], (C₆H₅)₃Sn have been prepared. The prepared compounds are investigated by different methods.     

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. 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.     

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. 91. Untersuchungen über N-Dicyandithiocarbamidsäure 4. Darstellung und Eigenschaften von Metall (I,II)-N-dicyandithiocarbamaten

On Chalcogenolates. 91. Studies on N-Dicyandithiocarbamic Acid. 4. Preparation and Properties of Metal (I,II) N-Dicyandithiocarbamates The prepared N-dicyandithiocarbamates M[S₂C-N(CN)₂] with M = Cu, Tl as well as M[S₂C-N(CN) ₂]₂ with M = Ba, Pb, Cd, Hg, Co have been investigated 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. 130. Untersuchungen über Rhodanine 1. Darstellung und Charakterisierung von Rhodanin und 5-Methylrhodanin

On Chalcogenolates. 130. Studies on Rhodanines 1. Synthesis and Characterization of Rhodanine and 5-Methyl Rhodanine The rhodanines with R ? H and CH₃ have been prepared by reaction of ammonium dithiocarbamate with the sodium salt of chloroacetic acid and 2-bromopropionic acid, respectively. The compounds have been characterized by means of spectroscopic 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, 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. 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. 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. 119. Untersuchungen über N-Nitrocarbamate,N-Nitrocarbamidsäure-O-ethylester und Salze dieses Esters. Versuche zur Darstellung von N-Nitrodithiocarbamaten

On Chalcogenolates. 119. Studies on N-Nitrocarbamates, O-Ethylester of N-Nitrocarbamic Acid, and Salts of this Ester. Attempts to Prepare N-Nitrodithiocarbamates The title compounds M₂[O₂CNNO₂] with M = Na, K, and O₂N? NH? CO? OC₂H₅ as well as M[O₂NNCO? OC₂H₅] with M = NH₄, K, Rb, Cs, Ag, and Hg[O₂NNCO? OC₂H₅]₂ have been prepared. The properties and the electron absorption, infrared, ¹H and ¹³C NMR, and mass spectra are reported and discussed. Attempts to synthesize N-nitrodithiocarbamates under variable conditions were unsuccessful.