Über Chalkogenolate. 140. Untersuchungen über Dialkylester von Chalkogenokohlensäuren. 3. S,Se-Dialkyldithiomonoselenocarbonate Existenzbeweis von Alkylselenoxanthaten [S2C?SeR]−

On Chalcogenolates. 140. Studies on Dialkyl Esters of Chalcogenocarbonic Acids. 3. S,Se-Dialkyl Dithiomonoselenocarbonates. Evidence for the Existence of Alkyl Selenoxanthates [S₂C? SeR]^? The esters RSe? CS? SR′ with R = R′ = C₂H₅, ⁿC₃H₇ as well as with R = ⁿC₃H₇ and R′ = C₂H₅ have been produced by three different methods. The compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H, ¹³C, and ⁷⁷Se), and mass spectra. The unstable alkyl selenoxanthates M[S₂C? SeR], where M = Na, K and R = C₂H₅, ⁿC₃H₇, are formed by reaction of carbon disulfide with the corresponding alkane selenolate. Freshly prepared they react with alkyl iodides R′I to yield RSe? CS? SR′.     

Über Chalkogenolate. 138. Untersuchungen über Dialkylester von Chalkogenokohlensäuren 1. O,Se-Dialkylmonoselenocarbonate

On chalcogenolates. 138. Studies on Dialkyl Esters of Chalcogenocarbonic A cids. 1. O, Se-Dialkyl Monoselenocarbonates The esters RSe? CO? OR′ with R = R′ = C₂H₅ as well as with R = ⁿC₃H₇ and R′ = CH₃, C₂H₅ have been prepared by reaction of sodium alkane selenolates with alkyl esters of chloroformic acid. The compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H, ¹³C, and ⁷⁷Se), and mass spectra.     

Über Chalkogenolate. 137. Isothiocyano-, Isothiocyanomonothio- und Isothiocyanodithio- ameisensäurealkylester

On Chalcogenolates. 137. Alkyl Esters of Isothiocyanoformic, Isothiocyanomonothioformic and Isothiocyanodithioformic Acids The esters RO? CO? NCS, where R = CH₃, C₂H₅, as well as RS? CO? NCS and RS? CS? NCS with R = C₂H₅, ⁿC₃H₇ have been prepared by three different methods. The reaction between the corresponding chloro compound and KSCN in the presence of the phase transfer catalyst 18-crown-6 gives the highest yields. The electron absorption, infrared, nuclear magnetic resonance, and mass spectra of these compounds are reported.     

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. 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. 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. 127. Diester der Cyaniminodiameisensäure NC?N(CO?OR)2 mit R = CH3, C2H5 und C6H5. Thiolyse der Diester

On Chalcogenolates. 127. Diesters of Cyanimino Diformic Acid NC? N(CO? OR)₂, where R = CH₃, C₂H₅, and C₆H₅. Thiolysis of these Diesters The diesters NC? N(CO? OR)₂ have been prepared by reaction of the sodium salt of cyanamide with the corresponding chloroformic acid ester. The thiolysis of these esters yields H₂N? CS? NH? CO? OR. The compounds with R = CH₃, C₂H₅, and C₆H₅ have been characterized by means of diverse methods.     

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.     

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.     

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. 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. 85. Untersuchungen über Halbester der Trithiokohlensäure 3. Schwingungsspektren von Alkylthioxanthogensäuren und Wasserstoffbrücken in den freien Säuren

On Chalcogenolates. 85. Studies on Hemiesters of Trithiocarbonic Acid 3. Vibrational Spectra of Alkyl Thioxanthic Acids and Hydrogen Bondings in the Free Acids The IR spectra of alkyl thioxanthic acids RS? CS(SH) with R = CH₃, C₂H₅, ⁿC₃H₇, ⁱC₃H₇, ⁿC₄H₉, ^sC₄H₉, ^tC₄H₉, and CH₃S? CS(SD) as well as the Raman spectrum of the Compound with R = CH₃ have been assigned. The formation of hydrogen bondings in the free acids has been studied by means of i.r. spectra, ¹H-n.m.r. spectra, and electron absorption spectra. The energies of the hydrogen bondings have been calculated.     

Über Chalkogenolate. 150. Reaktion von Formamid mit Kohlenstoffdisulfid 4. Ester der N-Formyldithiocarbamidsäure

On Chalcogenolates. 150. Reaction of Formamide with Carbon Disulfide. 4. Esters of N-Formyl Dithiocarbamic Acid The hitherto unknown esters of N-formyl dithiocarbamic acid H? CO? NH? CS? SR, where R ? CH₃ and C₂H₅, have been characterized by means of diverse spectroscopic methods.     

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. 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.     

Direktsynthese von orthometallierten Ketonen des Typs RCO (o-C6H4)Mn(CO)4−nLn (R = Alkyl- und Arylrest,n = 0, 1, 2, L = Ligand)

Direct Synthesis of Orthometallated Ketones of the Type RCO(o-C₆H₄)Mn(CO)_4?nL_n (R = Alkyl and Aryl Groups, n = 0, 1, 2, L = Ligand) The starting materials of the type RMn(CO)_5?nL_n und (C₆H₅)₂ Hg react to the products of the type RCO(o-C₆H₄)Mn(CO)_4?nL_n[n = 0, R = Ch₃, C₂H₅, C₃H₇, C₆H₅,CH₂; R = C₆H₅, n = 1, L = E(C₆H₅)₃, E = P, As, Sb; R = C₆H₅, n = 2, L = P(OR′)₃, R′ = C₆H₅, CH₃, C₂H₅, C₃H₇]. Steps of their complex reaction pathway are proposed. These orthometallated substances have been characterized by means of ¹H-n.m.r., i.r. and u.v. spectroscopic measurements. The determination of the molecular structure of the two compounds RCO(o-C₆H₄)Mn(CO)₃L [R = C₂H₅, L = CO; R = C₆H₅, L = As(C₆H₅)₃] show that both contain a planar heterocyclic five-membered ring of the type .     

Über organogermaniumtrisulfinsäureester und versuche zur darstellung von tetrasulfinsäureestern des germaniums

The trisulfinic esters of germanium RGe(O₂SR′)₃ (R = R′ = CH₃; R = C₆H₅, R′ = CH₃, C₂H₅), which are sensitive to hydrolysis and temperature, are obtained by reaction of the corresponding trichlorides RGeCl₃ with anhydrous silver sulfinates. Aromatic trisulfinic esters as well as tetrasulfinic esters of germanium could not be obtained because of steric reasons. The esters, in which the RSO₂^?-residues are linked to germanium via oxygen, are investigated on the basis of their ¹H NMR, mass, IR and Raman spectra.     

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. 142. Untersuchungen über Trimethylsilylxanthogensäure. 2. S-Methyl- und S-Ethyltrimethylsilylxanthat

On Chalcogenolates. 142. Studies on Trimethylsilyl Xanthic Acid. 2. S-Methyl and S-Ethyl Trimethylsilyl Xanthates The hitherto unknown S-alkyl trimethylsilyl xanthates (CH₃)₃SiO? CS? SR, where R = CH₃ and C₂H₅, have been characterized with electron absorption, infrared, nuclear magnetic resonance (¹H, ¹³C, and ²⁹Si), and mass spectra.     

Polymerization of cyclic esters of phosphoric acid. VI. Poly(alkyl ethylene phosphates). Polymerization of 2-alkoxy-2-oxo-1,3,2-dioxaphospholans and structure of polymers

Five-membered cyclic esters of phosphoric acid of the general formula: ? CH₂CH(R)OP(O)-(OR′)O? polymerize readily to solid, soluble polymers of high molecular weight without any rearrangement known for various tri- and pentavalent organophosphorus monomers. ¹H-, ¹³C-, and ³¹P-NMR spectra of polymers confirmed their linear structure: where R is H, with R′ = CH₃, C₂H₅, n-C₃H₇, i-C₃H₇; n-C₄H₉, CCl₃CH₂, or C₆H₅, or R is CH₂Cl and R′ is C₂H₅. The use of n-C₄H₉Li, (C₅H₅)₂Mg, or (i-C₄H₉)₃Al as initiators leads to polymers with M _n = 10⁴–10⁵.