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. 158. Reaktion von N-Methylthioformamid mit Kohlenstoffdisulfid 2. Oxydation von N-Methyl-N-thioformyldithiocarbamaten und S-Methylester der N-Methyl-N-thioformyldithiocarbamidsäure

On Chalcogenolates. 158. Reaction of N-Methyl Thioformamide with Carbon Disulfide. 2. Oxidation of N-Methyl N-Thioformyl Dithiocarbamates and S-Methyl Ester of N-Methyl N-Thioformyl Dithiocarbamic Acid The oxidation of N-methyl N-thioformyl dithiocarbamates with iodine forms the hitherto unknown N-methyl-1,2,4-dithiazole-3,5-dithione . The S-methyl ester of N-methyl N-thioformyl dithiocarbamic acid H? CS? NCH₃? CS? SCH₃ has been prepared by reaction of potassium N-methyl N-thioformyl dithiocarbamate with methyl iodide as well as by reaction of the S-methyl ester of N-methyl N-formyl dithiocarbamic acid with Lawesson reagent. Both compounds have been characterized by means of chemical and diverse spectroscopic 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. 126. Untersuchungen über N-Cyanformamidinodithiocarbimidsäure 2. Thermisches Verhalten von Kalium-N-cyanformamidinodithiocarbimat in Lösung

On Chalcogenolates. 126. Studies on N-Cyanformamidino Dithiocarbimic Acid. 2. Thermal Behaviour of Potassium N-Cyanformamidino Dithiocarbimate in Solution The thermal treatment of K₂[S₂C?N? C(NH₂)?N? CN] in methanolic solution yields . The semi-hydrate has been isolated. It reacts with acid to form The reaction with H₃CI gives The compounds have been characterized by means of electron absorption, ¹H- and ¹³C-N.M.R., infrared, 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.     

Thermische Zerfallsreaktionen von Nitroverbindungen in Stosswellen. II: Dissoziation von Nitroäthan

A shock wave study of the thermal decomposition of nitroethane in excess Ar at temperatures 900 < T < 1350 K and total concentrations of 4,5 · 10^?6 < [Ar] < 3 · 10^?4 mol cm^?3 showed that the C? N-bond fission is the primary reaction step. This unimolecular reaction could be observed in its transition region near the high pressure limit. The derived rate constants are k_∞ = 10^15.9 exp (–57 kcal mol^?1/RT) s^?1 for the high pressure and k₀/[Ar] = 10^18.0 exp (-36 kcal mol^?1/RT) cm³ mol^?1 s^?1 (at T ? 1100–1200 K) for the low pressure limit. The observed concentration profiles of C₂H₅NO₂ and NO₂ permitted to conclude on the subsequent decomposition of the ethyl radical This reaction was found to be in the fall-off range under the applied conditions.     

Über Oberflächenverbindungen von Übergangsmetallen. VIII. Die Komplexbildung von koordinativ ungesättigtem Oberflächen-Chrom (II) mit Oxiden des Stickstoffs

On Surface Compounds of Transition Metals. VIII. Complex Formation of a Coordinatively Unsaturated Cr^II Surface Compound with Nitrogen Oxides N₂O forms with surface-Cr(II) a relatively unstable light blue compound of the stoichiometry 1:1, while addition of NO results in formation of a very stable dark brown, diamagnetic surface complex . By reaction with O₂ this complex undergoes — depending on reaction temperature — either replacement of NO unter reoxidation of the metal (→Cr(VI)) or/and reaction of the ligand (→NO₂). Direct reaction of NO₂ with results in the same products as stepwise addition of NO and 1/2 O₂. reacts with HCl/ROH under formation of the soluble, paramagnetic kation [Cr(NO)(ROH)_n]²⁺, which is formulated as [Cr(II)(NO)]²⁺ ? [Cr(I)(NO⁺)]²⁺ accordingly to the e.s.r. 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. 112. Methylester von Dithiocarbamidsäuren

On Chalcogenolates. 112. Methylesters of Dithiocarbamic Acids The infrared spectra, nuclear magnetic resonance (¹H) spectra, and mass spectra of are communicated.     

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.     

Zur Zersetzung von Tetrathiowolframaten und Bildung von Nonathiotriwolframaten

Decomposition of Tetrathiotungstates and Formation of Nonathiotritungstates The tetrathiotungstates have been prepared by reaction of [NH₄]₂WS₄ with [R₄X]Y (Y = OH, Cl or I). The tetrathiotungstates decompose under variable conditions to form [R₄X]₂W₃S₉. The thiotungstates [R₄X]₂WS₄ and [R₄X]₂W₃S₉ have been characterized by chemical and thermoanalytical methods as well as by infrared, electron absorption, ¹H-NMR, and mass spectra. The decomposition of [R₄N]₂WS₄ has been studied kinetically. A mechanism of the formation of W₃S₉^2? is suggested.     

Fluorierung von Dioxa- und Oxazaphospholanen

Fluorination of Dioxa- and Oxazaphospholanes The fluoridolysis of cyclic esters and esteramides of phosphorous acid ( 1 , 2 , 4 , 5 , 7 , 11 , and 12 ,) using the acid fluorination reagent Et₃N · nHF (n > 1) or an excess of a basic composed agent (n < 1) yields in all cases HPF₅^? ( 3 ,). With stoichiometric amounts of fluoride, however, the fluorophospholanes ( 4 ,) and ( 5 ,) as well as fac.- and mer.-o- ( 6a, 6b ,) and the spirocyclic fluorohydridophosphate ( 8 ,) are obtained. ( 13 ,) reacts to ( 14 ,) and the spirocyclic compound ( 15 ,) gives ( 16 ,). The fluorophosphoranes ( 18 ,), ( 19 ,), and ( 21 ,) are obtained by oxidative fluorination of the spiro- or bicyclic P? H compounds 11, 12 , and 20 , with CCl₄/Et₃N · nHF (n < 1). The oxidative fluorination of the cyclic triesters of phosphorous acid 7 , and 23 , leads to the cyclic fluorophosphates ( 22 ,) and 16 , as well as 6. , The compounds 18, 19 , and 22 , are also formed by oxidative fluorination of elemental phosphorus, P₄, in the presence of the corresponding bifunctional nucleophile.     

Beiträge zur Chemie der Phosphinalkylene—VII: NMR-Daten von Dimethylamino-methylen-phosphoranen

¹H and ³¹P? NMR parameters are reported for dimethyl-aminomethylene phosphoranes (1 to 4). The reaction of with NaNH₂ gives 4 .     

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.     

Absolute rate constants for reactions of free radicals in the high-temperature photolysis of formamide vapor. II. Amino radicals

The rotating-sector method has been applied to the photoinitiated radical-chain decomposition of formamide at 300°C to measure the rate constant for the bimolecular disappearance of NH₂ radicals. The decomposition is propagated by the reactions (1) (2) Conditions were chosen so that reaction (1) was rate controlling and NH₂ the terminating radical. A flow system was employed with C₂F₆ as a carrier gas at a pressure of 300 Tort, and the chain reaction was initiated by the photolysis of either formamide or NH₃. A value of 4.7(±2.0) × 10¹⁰ (M ·sec)^?1 was estimated for the termination reaction (3) and a value of 8.4 × 10⁶ (M ·sec)^?1 for reaction (1) in the same system, both at 300°C.     

Kristallstruktur und elektrische Leitfähigkeit von Li2–2xMn1+xCl4-Spinelltyp-Mischkristallen

Crystal Structure and Electric Conductivity of Spinel-Type Li_2–2xMn_1+xCl₄ Solid Solutions The electric conductivity of the fast lithium ion conductors Li_2–2xMn_1+xCl₄ was measured by impedance spectroscopic methods. The conductivities obtained, e.g. ～ 4 × 10^?1 Ω^?2 cm^?1 at 570 K, depend only little on the lithium content. The crystal structure of Li_1.6Mn_1.2Cl₄ was determined by neutron powder and X-ray single crystal diffraction (space group Fd3 m, Z = 8, a = 1 049.39(6) pm, R_w = 1.4% on the basis of 170 reflections). The lithium deficient chloride crystallizes in an inverse spinel structure like the stoichiometric compound Li₂MnCl₄ according to the formula (Li_0,8)[Li_0,4Mn_0,6]₂Cl₄ with vacancies ( ) at the tetrahedral sites. The decrease of the M_oct? Cl distances with the increase of x reveals that the ionic radius of Mn²⁺ in chlorides is equal or even smaller than that of Li⁺ opposite to fluorides and oxides. The ? Cl distances of spinel type chlorides are 237 ( _tet) and 274 pm ( _oct), respectively. The mechanism of the ionic conductivity is discussed.     

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.     

Zur Kenntnis der Chemie der Metallcarbonyle und der Cyanokomplexe in flüssigem Ammoniak. XXXI. Über die Reaktionen von kationischen η5-Cyclopentadienylmolybdäncarbonyl-Komplexen mit flüssigem Ammoniak

The Chemistry of Metal Carbonyls and Cyano Complexes in Liquid Ammonia. XXXI. On the Reactions of Cationic η⁵-Cyclopentadienyl-molybdenumcarbonyl Complexes with Liquid Ammonia Depending on the reaction conditions, the cationic complexes [η⁵-C₅H₅Mo(CO)₃L]⁺ (L = NH₃, PPh₃, CO) react with liquid ammonia according to: The characteristics and reactivities of the new carbomoyl derivatives are described.     

A quantitative study of alkyl radical reactions by kinetic spectroscopy. II. Combination of the methyl radical with the oxygen molecule

The kinetics of the reaction have been studied, using the technique of flash photolysis and kinetic spectroscopy to follow the methyl radical concentration. The order of the reaction lies between 2 and 3 throughout the range of pressure from 25 to 380 torr at 22°C, and the results are consistent with a single reaction sequence: The limiting values of the third-order rate coefficients at low pressures are (3.6±0.3) × 10¹¹ 1.² mole^?2 sec^?1 when M is neopentane, and (0.94 ± 0.03) × 10¹¹ 1.² mole^?2 sec^?1 when M is nitrogen. The limiting value of the second-order rate coefficient at high pressures is (3.1 ± 0.3) × 10⁸ 1. mole^?1 sec^?1. The rate constant for the independent second-order reaction is shown to be not much greater than 2 × 10⁵ 1. mole^?1 sec^?1, so that this reaction does not complete significantly with the combination reaction. This new interpretation is contrary to currently accepted views.