Über die Darstellung von Verbindungen des Typs Cl3VNR

The reaction of VOCl₃ with sily-substituted amines results in the substitution of oxygen in VOCl₃ and in compounds of type Cl₃V = NR. In this way, we succeeded in isolating the pure compound Cl₃V = NCH₃ (I). The existence of compound (Cl₃VNC₆H₅)_x (II) was proved by direct synthesis from Cl₃VO and ((CH₃)₃Si)₂NC₆H₅, and by the decomposition of the new addition compounds Cl₃VO · 2 OCNC₆H₅ (III) and Cl₃VO · 2 OSNC₆H₅ (IV).     

Zur Kenntnis der Chemie der Silazane. IV. Über ein Sulfurylphosphazo-silazan

Trichlorophosphazo-sulphurylchloride. Cl₃P?N? SO₂Cl, reacts with heptamethyldisilazane to yield the Si? N? P compound (I) formulated in ?Inhaltsübersicht”?. (I) reacts with PCl₅ or C₆H₅? PCl₄ forming the known 2,2,2,4,4,4-hexachloro-1,3-di-methylcyclo-diphosphazane(II), accompanied by the compound Cl₃P?N? SO₂Cl and C₆H₅? PCl₂?N? SO₂Cl, respectively, which were detected by means of ³¹P-NMR spectroscopy.     

Über Phosphorstickstoff-Verbindungen XXVIII. Über Reaktionen von Cyanamid,Dicyanimid und Dicyandiamid mit PCl5

Interaction between cyanamide and PCl₅ in the mole ratio 1:3 yields the phosphazenium salt [Cl₃P?N? C(Cl)?N? PCl₃] [PCl₆]. The reaction of sodium dicyanimide and PCl₅ gives 1. 1. 3. 5-tetrachloro-1-phospha-2. 4. 6-triazine (compound B in ?Inhaltsübersicht”?). Dicyandiamide and PCl₅ (1:2) give compound C and, at milder conditions the salt-like phosphatriazine D. Solvolysis of C with formic acid or of D with sulphur dioxide yields E.     

Über Phosphorstickstoffverbindungen. XXXIII. Reaktionen von Diphenyltrichlorphosphoran mit Hydraziniumsalzen und -derivaten

Hydrazinium monochloride disproportionates on interaction with diphenyl-trichlorophosphorane, giving N₂ and [(C₆H₅)₂P(Cl)? N? PCl(C₆H₅)₂]Cl. The phosphinazine dihydrochloride [(C₆H₅)₂PCl? NH? NH? PCl(C₆H₅)₂]Cl₂ is obtained according to equation (4). The preparation of the P? N five-ring compound X, formulated in ?Inhaltsübersicht”?, is described.     

Über Oxocuprate. XI. Zur Kenntnis von Ba3Cu2O4Cl2

On Osocuprates. XI. Ba₃Cu₂O₄Cl₂ A new oxohalogenocuprat, Ba₃Cu₂O₄Cl₂ mas prepared and investigated by X-ray single crystal methods. The hitherto unknown compound has orthorhombic symmetry (Space group: D_2h⁵—Pmma; a = 6.653, b = 6.000, c = 10.563 Å). It shows angled chains of O^2?-squares around Cu²⁺. One of the Cu²⁺ positions is completed by Cl^minus; to a tetragonal pyramid. The coordination polyhedrals of Ba_I–III and the connection with the Cu/O-chains are described and discussed.     

Über Chalkogenolate. 113 Umsetzung von Chloramin mit Kohlenstoffdisulfid und mit Methylestern von Dithiocarbamidsäuren

On Chalcogenolates. 113. Reactions of Chloramine with Carbon Disulfide and with Methylesters of Dithiocarbamic Acids The reactions of chloramine with CS₂ and with H₂N? CS? SCH₃, CH₃? NH? CS? SCH₃, and (CH₃)₂N? CS? SCH₃ have been studied. The reaction with the methylester of dithiocarbamic acid gives the known dimethyl perthiocyanate and the reaction with the methylester of N-methyldithiocarbamic acid leads to CH₃S? CS? N(CH₃)? C(?NCH₃)? SCH₃. The latter compound has been characterized by means of electron absorption spectra, infrared spectra, nuclear magnetic resonance spectra (¹H and ¹³C), and mass spectra.     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. I

The compound [HCCl=C(NPCl₃)(PCl₃)[PCl₆], VI, is formed in the reaction between acetonitrile and PCl₅. Reaction of H₂S with VI results in the formation of the chloride and by further reactions of this chloride with BCl₃ and SbCl₅ the tetrachloroborate and hexachloroantimonate salts respectively, are obtained. Chloroacetonitrile can be made to react with PCl₅ to give HCCl?C(NPCl₃)Cl, II, by use of suitable conditions. There is no indication that mixtures of cis/trans isomers of VI or II exist as has been previously postulated. The ¹H and ³¹P NMR spectra of the above-mentioned compounds and numerous further products from the reactions of CH₃CN, ClCH₂CN and Cl₂CHCN with PCl₅ are discussed in detail. II occurs in a cisoid and a transoid conformation.     

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 die Umsetzung von Adipinsäurediamid mit Phosphorpentachlorid

Reaction of Adipic Acid Diamide with Phosphorus Pentachloride The reaction of adipamide (I) with phosphorus pentachloride in a solvent leads to (Cl₃P?NCCl₂CCl₂CH₂)₂ (II). The stages of the reaction are: 1. chlorination of the keto and methylen groups 2. formation of the ? N?PCl₃ group. This result is a supplement of the existing conception about the course of the reaction of carboxylic acid amides with phosphorus pentachloride. The reaction of (I) with PCl₅ without any solvent has been reproduced and the course of reaction has also been investigated. This reaction gives mainly NC(CH₂)₄CN. The resulting product of a careful hydrolysis of (II) is (Cl₂OPN?CClCl₂CH₂)₂. A total hydrolysis gives back (I).     

Bindungsenergien von Phosphor–Stickstoff-Bindungen

The enthalpies of formation of P? N compounds with three-, four-and five-coordinated phosphorus have been determined by combustion calorimetry. From these data, using the energy values for atomisation, the P? N bond energies have been estimated to be 69 Kcal/Mole for P₄(NCH₃)₆ with three-coordinated P, and 79 Kcal/Mole for [PhNHP(O)NPh]₂ with tetrahedral phosphorus. For the compound C₂H₆Cl₆N₂P₂, in which the phosphorus is in a trigonal-bipyramidal hybrid function, the axial P? N bond energy is estimated to be 69 Kcal/Mole, and the equatorial one 77.5 Kcal/Mole.     

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. 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.     

Bildung und NMR-spektroskopische Charakterisierung von Alk-(ar-)oxyderivaten von Trichlorphosphazen-N-phosphoryldichlorid,Cl3PN?P(O)Cl2, Imido- und N-Methylimidodiphosphoryltetrachlord,Cl2P(O)NHP(O)Cl2 bzw. Cl2P(O)N(CH3)P(O)Cl2

Formation and N.M.R.-Spectroscopic Characterization of Alk-(ar-)oxy Derivatives of Trichlorophosphazene-N-phosphoryldichloride, Cl₃P?N? P(O)Cl₂, Imido- and N-Methylimidodiphosphoryltetrachloride, Cl₂P(O)NHP(O)Cl₂ and Cl₂P(O)N(CH₃)P(O)Cl₂ The ester chlorides and esters P₂NOCl_5?x(OR)_x (x = 1?5), P₂(NH)O₂Cl_4?x(OR)_x (x = 1–4) and P₂(NCH₃)O₂Cl_4–x(OR)_x (x = 1–4) derived from the title compounds by substitution of chlorine atoms by alk- or aroxy groups are characterized by their ³¹P-n.m.r. data. The possibilities for forming these compounds by alcoholysis, chloridolysis, dealkylation and P? N-bond formation are discussed.     

Über Phosphorstickstoffverbindungen. XXX. Ein neues fünfgliedriges Ringsystem mit Stickstoff,Phosphor und Kohlenstoff im Ring

Diphenylthiosemicarbazide reacts with PCl₃ to form the fivemembered cyclic system Ia (see ”?Inhaltsübersicht?), whereas with PCl₅ the compound II is formed. With PCl₅ Ib is formed from Ia, with Cl₂ II.     

Übergangsmetall-carben-Komplexe. LXXX. α-Alkoxy- und α,α-dialkoxysubstituierte Phenylacetyl-(pentacarbonyl)metallate und Pentacarbonyl[alkoxy(benzyl)-carben]-Komplexe des Chroms und Wolframs

Vibrational Spectra of Dichlorophosphorylmethylamine CH₃? NH? P(?O)Cl₂ and its Adducts with SbCl₅ and SnCl₄ The vibrational spectra of liquid samples and solutions, as well as cryoscopic molecular weight determinations show that CH₃? NH? P(?O)Cl₂ exists largely in the dimeric form. The association occurs through hydrogen bridges. The adducts SbCl₅ · CH₃? NH? P(?O)Cl₂ and SnCl₄ · 2 CH₃? NH? P(?O)Cl₂ are formed through addition via an oxygen atom. The ligands have cis-configuration in the tin compound.     

Über Chalkogenolate. 201. Untersuchungen über Selenformamide

On Chalcogenolates. 201 Studies on Selenoformamides The yellow selenoformamides H? CSe? NH₂, H? CSe? NH? CH₃, and H? CSe? N(CH₃)₂ have been prepared by reaction of the corresponding formamide with P₂Se₅. The compounds have been characterized by means of electron absorption, infrared, and nuclear magnetic resonance spectra. The decomposition of the selenoformamides in ethanolic solution has been studied kinetically at 20.0°C. The preparation of selenoformyl dithiocarbamates was not successful.     

Über Bleisilberphosphate mit Apatitstruktur

On Lead Silver Phosphates with the Apatite Structure The hitherto unknown leas silver phosphate (Pb₈Ag₂PO₄)₆ has been prepared. It has an apatite structure with unoccupied halide positions like the analogous lead alkali compounds and forms solid solutions with Pb₁₀(PO₄)₆O, Pb₁₀(PO₄)₆(OH)₂, and Pb₁₀(PO₄)₆Cl₂. At 800°C, Pb₈Ag₂(PO₄)₆ decomposes to solid Pb₃(PO₄)₂ and PbAgPO₄. (Pb, Ag) apatites have been precipitated from aqueous solutions. On the side being richer in Ag they can approximately be formulated as solid solutions between Pb₈Ag₂(PO₄)₆ and Pb₁₀(PO₄)₆(OH)₂. However, the i.r. spectrum reveals clear differences compared with thermal and hydrothermal preparations. The distribution of cations shows nonideal behaviour with reduced tendency for fixation of Ag⁺, if the content of Ag in the precipitate is high. The compound PbAgPO₄ decomposes below 520°C to Pb₈Ag₂(PO₄)₆ and Ag₃PO₄. The arsenate apatite Pb₈Ag₂(AsO₄)₆ decomposes below 530°C to Pb₃(AsO₄)₂ and Ag₃AsO₄.     

Über Chalkogenolate. 178. Untersuchungen über Kupfer(I)-ethylxanthat

On Chalcogenolates. 178. Studies on Copper(I) Ethyl Xanthate Yellow Cu[S₂C? OC₂H₅] has been prepared by two different methods. In contrast to earlier observations it is not soluble in ethanolic solutions containing [S₂C? OC₂H₅]^? ions in excess. Cu[S₂C? OC₂H₅] reacts with CS₃^2? ions to form [Cu(CS₃)]^?. The compounds [(C₆H₅)₄E][Cu(CS₃)] with E = P, As have been isolated.     

Über Reaktionen des P4S10 mit siliciumorganischen Verbindungen

Reactions of P₄S₁₀ with Organosilicon Compounds P₄S₁₀ ( 1 ) can be degraded with silicon-nitrogen compounds. 1 reacts with (CH₃)₃Si? N(CH₃)₂ ( 2 a ) and (CH₃)₃Si? N(C₂H₅)₂ ( 2 b ) to yield S?P[N(CH₃)₂]₂SSi(CH₃)₃ ( 3 a ) and ( 3 b ). By the reaction of 1 with [(CH₃)₃Si]₂S ( 4 ) S?P[S? Si(CH₃)₃]₃ ( 6 ) is formed in high yield. (C₆H₅PS₂)₂ ( 7 ) was used as a model to investigate the course of the reaction. This leads to C₆H₅P(S)? [N(CH₃)₂]SSi(CH₃)₃ ( 9 ) and C₆H₅P(S)[SSi(CH₃)₃]₂ ( 10 ). The reaction mechanism will be discussed. The n.m.r. data and mass spectra are reported.     

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.