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. 180. Methoxythiocarbonyl-methylsulfane CH3O?CS?Sx?CH3 mit x = 1, 2 und Methylthiothiocarbonyl-methylsufane CH3S?CS?Sx?CH3 mit x = 1, 2

On Chalcogenolates. 180. Methoxythiocarbonyl Methyl Sulfanes CH₃O? CS? S_x? CH₃ with x = 1, 2 and Methylthiothiocarbonyl Methyl Sulfanes CH₃S? CS? S_x? CH₃ with x = 1, 2 The monosulfanes have been prepared by known procedures. For the first time the disulfanes have been synthesized by reaction of K[S₂C? OCH₃] and K[S₂C? SCH₃] with the S-methyl ester of methanethiosulfonic acid CH₃? SO₂? SCH₃. The sulfanes CH₃O? CS? S_x? CH₃ and CH₃S? CS? S_x? CH₃, where x = 1 and 2, have been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra.     

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. 181 [1]. Thiocarbamoyl-methylsulfane

On Chalcogenolates. 181. Thiocarbamoyl Methyl Sulfanes The thiocarbamoyl methyl sulfanes H₂N? CS? S_x? CH₃? NH? CS? S_x? CH₃, and (CH₃)₂N? CS? S_x? CH₃ with x = 1 and 2 have been prepared by known procedures (for x = 1) and by reaction of the corresponding dithiocarbamate with the S-methylester of methanethiosulfonic acid CH₃? SO₂? SCH₃ (for x = 2). The compounds have been studied by means of diverse spectroscopic methods.     

Untersuchungen über das Reaktionsverhalten von Antimonpentachlorid. III [1]. Zur Reaktion von Antimon (V)-chlorid mit Methylisocyanat

Studies on the Reactivity of Antimony Pentachloride. III. The Reaction of Antimony(V) Chloride and Methylisocyanate Methylisocyanate CH₃NCO reacts with SbCl₅ in boiling CCl₄ by an insertion-reaction to a product of the formula C₅H₆Cl₉N₂O₂Sb I, which has the chlorformamidinium-structure (Cl? C(O)? N(CH₃)? CCl? N(CH₃)? C(O)? Cl)⊕SbCl₆?. Hydrolysis of I yields the heterocycle C₅H₆N₂O₄ II. The reaction with methanol gives (CH₃? NH? CCl? NH? CH₃)⊕SbCl₆? III and (CH₃? NH? CCl? N(CH₃)? C(O)? OCH₃)⊕SbCl₆? IV. The i.r. and Raman spectra of the compounds I, III and IV are discussed.     

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. 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.     

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. 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.     

Kristall- und Molekülstruktur von Tetra-n-butylammonium-N-methyl-N-thioformyldithiocarbamat

Crystal and Molecular Structure of Tetra-n-butylammonium N-Methyl-N-Thioformyl Dithiocarbamate [N(n-C₄H₉)₄][S₂C? N(CH₃)? CS? H] crystallizes in the triclinic space group P1 (Z = 2) with cell dimensions (?45°C) a = 9.185(2) Å, b = 10.263(3) Å, c = 13.301(3) Å, α = 101.73(2)°, ß = 99.59(2)°, γ 100.57(2)°. The crystal structure was solved by means of direct methods and refined to a conventional reliability index R = 0.066 (R_ω = 0.070). 5945 independent intensities being measured.     

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.     

Umsetzungen von Tetrafluor-1,2-ethandisulfenyldichlorid mit Ketonen und Olefinen

Reactions of Tetrafluoro-1, 2-ethanedisulfenyldichloride with Ketones and Olefines The reaction of ClSCF₂CF₂SCl 1 with (CH₃)₃C? C(O)CH₃, hexene, diacetyl, cyclobutanone, and H₂C?CHC(O)CH₃ leads to the cyclic and acyclic products 2 – 6 . They are destillable liquids, which have been characterized on the basis of elemental analysis, mass spectra, ¹⁹F-, ¹³C-, and ¹H-n.m.r. spectra. The reaction mechanism will be discussed.     

Über Chalkogenolate. 129. Untersuchungen über Ester der N-Cyancarbamidsäure. 2. Darstellung,spektroskopische Charakterisierung und Zersetzung von O-Methyl- und O-Ethyl-N-cyancarbamat

On Chalcogenolates. 129. Studies on Esters of N-Cyancarbamic Acid. 2. Synthesis, Spectroscopic Characterization, and Decomposition of O-Methyl and O-Ethyl N-Cyancarbamate NH₄[NC? N? CO? OR], where R = CH₃ and C₂H₅, reacts with acids to yield unstable NC? NH? CO? OR. The esters decompose to form NC? N?C(NH₂)? NH? CO? OR. The compounds have been characterized by means of electron absorption, ¹H and ¹³C NMR, infrared, and mass spectra.     

Über Chalkogenolate. 159. Umsetzung von 1,2-Ethandithiolaten mit Kohlenstoffdisulfid 1. Darstellung und Eigenschaften von 1,2-Ethan-bis(trithiocarbonaten)

On Chalcogenolates. 159. Reaction of 1,2-Ethanedithiolates with Carbon Disulfide. 1. Synthesis and Characterization of 1,2-Ethane-bis(trithiocarbonates) The reaction of 1,2-ethanedithiolates with carbon disulfide forms the corresponding 1,2-ethane-bis(trithiocarbonates). The compounds M₂[S₂C? SCH₂CH₂S? CS₂] with M = Li, Na, K, Rb, Cs, NH₄, Tl 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. 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. 174. Reaktion von Acetamidin mit Kohlenstoffdisulfid 3. Kristallstruktur von Acetamidinium-N-acetimidoyldithiocarbamat [1]

On Chalcogenolates. 174. Reaction of Acetamidine with Carbon Disulfide. 3. Crystal Structure of Acetamidinium N-Acetimidoyl Dithiocarbamate The title compound [(H₂N)₂C? CH₃][S₂C? N?C(CH₃)? NH₂] crystallizes with Z = 4 in the monoclinic space group P2₁/n with cell dimensions a = 10.354(1), b = 6.798(1), c = 14.013(1) Å, β = 103.32(1)°. The crystal structure has been determined from single crystal X-ray data measured at 20°C and refined to a conventional R of 0.049 for 2 521 independent reflections (R_w = 0.052). The cation is associated with one anion by hydrogen bridges S…H? N and N…H? N forming an 8-membered ring system. The anion is not plane in contrast to hitherto known structures of dithiocarbamates.     

Über Chalkogenolate. 205. Reaktion von Acetamid mit Kohlenstoffdisulfid 2. Ester der N-Acetyldithiocarbamidsäure

On Chalcogenolates. 205. Reaction of Acetamide with Carbon Disulfide. 2. Esters of N-Acetyl Dithiocarbamic Acid The prepared yellow esters of N-acetyl dithiocarbamic acid H₃C? CO? NH? CS? SR with R = CH₃, C₂H₅ have been characterized by means of mass, electron absorption, infrared, and nuclear magnetic resonance spectra.     

Zur Umsetzung von Bis(2-mercaptoethyl)phosphinen mit Organozinn-Verbindungen Molekülstruktur eines zinnhaltigen Sechzehnringes

Reaction of Bis(2-mercaptoethyl)phosphines with Organotin Compounds. Molecular Structure of a Tin Containing Sixteen-membered Ring The reaction of bis(2-mercaptoethyl)phosphine with di-t-butyltin dimethoxide yields mixture of oligomers of the type [t-Bu₂Sn(SCH₂CH₂)₂Pr]_n (R ? Me, Ph) from which the trans-configurated dimers (n = 2) have been isolated. By the reaction with sulphur and selenium, respectively, these dimers were transformed to the corresponding thioxo and selenoxo derivatives. The sixteen-membered ring trans-[t-Bu₂Sn(SCH₂CH₂)₂P(S)Ph]₂ crystallizes in the space group P2₁/n with the unit cell dimensions a 1350.9, b 1310.2, c 1500.3 pm, β 96.36° and does not exhibit any intramolecular Sn? P interaction: The 1,5-diorgano-1-chloro-5-elementa-1-stanna(IV)-bicyclo-[3.3.0^1,5]octanes R(Cl)Sn(SCH₂CH₂)₂E ( 6 , R ? Ph, E ? PPh; 7 , R ? Ph, E ? NMe) have been prepared from the corresponding sodium dithiolates and phenyltrichlorostannane. The transannulare Sn? P and Sn? N interactions in 6 and 7 are confirmed by ³¹P and ¹¹⁹Sn NMR investigations.     

Über Chalkogenolate. 100. Untersuchungen über Monothiocarbamidsäure. 2. S-Methyl- und O-Methylmonothiocarbamat, 2,4,5-Trioxo-thiazolidin-(1,3)

On Chalcogenolates. 100. Studies on Monothiocarbamic Acid. 2. S-Methyl and O-Methyl Monothiocarbamate, 2,4,5-Trioxo-thiazolidine-(1,3) The methyl esters of monothiocarbamic acid H₂N? CO? SCH₃ and H₂N? CS? OCH₃ as well as 2,4,5-trioxo-thiazolidine-(1,3) and its potassium salt have been prepared and characterized by means of electron absorption, infrared, ¹H-NMR, and mass spectra.     

Substitutionsreaktionen mit Schwefeldiimiden

Substitution Reactions with Sulphur Diimides Substituted sulphur diimides are obtained by the reactions of (CH₃)₃Si? N?S?N? Si(CH₃)₃ with CH₃SO₂Cl and CCl₃SCl or with P₂O₃F₄ and (CH₃)₃Si? N?S?N? SN(CH₃)₂. S₄N₄ reacts with (CH₃)₂Si[N(CH₃)₂]₂ to from (CH₃)₂Si(N(CH₃)₂)? N?S?N? SN(CH₃)₂ while S₃N₂Cl₂ yields (CH₃)₂Si(Cl)? N?S?N? SN(CH₃)₂. It is possible to substitute the chlorine atom by diethylamine in the last compound. The new compounds are intermediates for the syntheses of cyclic sulphur-nitrogen compounds. They were characterized by mass-, ir-, ¹H-nmr spectra and elemental analysis.