Zur Reaktion von Imidodiphosphoryltetrachlorid mit Phosphorpentachlorid

Reaction of Imidodiphosphoryl Tetrachloride with Phosphorus Pentachloride Imidodiphosphoryl tetrachloride quantitatively reacts with PCl₅ to form, HCl, POCl₃, and Cl₃P?N? POCl₂. The mechanism of the reaction is discussed. Using ³²P-labeled PCl₅ was proved that the attack of the PCl₅ to imidodiphosphoryl tetrachloride does occur about an oxygen atom.     

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 sechsgliedrige Heterocyclen mit Phosphor-, Stickstoff- und Schwefelatomen im Ring

Cyclic sulphurylphosphazochloride (I: formula see ?Inhaltsübersicht”?) reacts with ammonia or methylamine forming the. tetramide(II) and (III), respectively, and with aniline or dimethylamine forming the diamide (IV) resp. (V). The synthesis of the diphenyl derivative (VI) is achieved starting from C₆H₅? PCl₄. (II) gives with PCl₅ the ionic compound (VII).     

Über die Reaktion von Phosphorpentachlorid mit den BF3-Addukten primärer Amine

Reaction of CH₃NH₂ · BF₃ and PCl₅ yields CH₃N(PCl₃)(BCl₃), (I), the behaviour of which to PCl₅, pyridine and H₂S is described. By using smaller amounts of PCl₅, CH₃N(PCl₃)(BCl₂F) (VI) is obtained. C₆H₅NH₂ · BF₃ reacts with PCl₅ to give C₆H₅N(PCl₃)(BCl₃) (IX). Physical data, especially the NMR spectra of the new compounds, are given and discussed.     

Synthese linearer und verzweigter Phosphazene aus N-silylierten Phosphorylamiden

Synthesis of Lineary and Branched Phosphazenes from N-silylated Phosphoryl Amides The use of N-silylated phosphoryl amides in the reaction with PCl₅ favours the KIRSANOV reaction and reduces undesirable substitution reactions. However, silylated monoamides, X₂P(O)NHSiMe₃ (X = OEt, NEt₂), do not give the expected trichlorophosphazenes but the isomeric N-dichlorophosphoryl phosphazenes, Cl₂P(O)? N?PClX₂, which are also formed in the reaction of (EtO)₂P(O)NCl₂ with PCl₅. As the first phosphoryl-P, P-bis(trichlorophosphazene) (EtO)P(O)(N?PCl₃)₂ could be obtained in the reaction of PCl₅ with the silylated diamide (EtO)P(O)(NHSiMe₃)₂. Tris reactivity of silylated amides to P? Cl compounds decreases in the row PCl₅ > POCl₃ > CIP(O)(OEt)₂ > ClP(O)(NEt₂)₂. In the reaction with phosphoryl chlorides the preferred formation of compounds with P? NH? P bridges could not be observed.     

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 die Reaktion von Phosphorpentachlorid mit den BF3-Addukten sekundärer und tertiärer Amine

Reaction of F₃B · NH(CH₃)₂ with PCl₅ yields [(CH₃)₂NPCl₃][BCl₄] (I), which can also be obtained by reaction of [(CH₃)₂NBCl₂]₂ with PCl₅. In BF₃ · N(CH₃)₃ the fluorine atoms are exchanged with chlorine atoms, by PCl₅, ³¹P, ¹⁹F, and ¹¹B-NMR spectra of the reactions products are described and discussed.     

Phenylphosphonsäure-bis(methylamid) und seine Reaktionen mit Phosphor(III)-Halogeniden

Phenyl Phosphonic Bis(methylamide) and its Reactions with Phosphorus (III) Halides Preparation of phenyl phosphonic bis(methylamide), I , from phenyl phosphonic dichloride and methylamine is described. I is characterized by its nmr, mass, and vibration spectra and by its reactions with PCl₃, CH₃PCl₂, and C₆H₅PCl₂. The two reactions mentioned last yield C₆H₅P(O)[N(CH₃)P(CH₃)Cl]₂ ( IIIa ) and C₆H₅P(O)[N(CH₃)P(C₆H₅)Cl]₂ ( IIIb ), respectively.     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. III. Die Reaktion zwischen Acrylnitril und PCl3

On Trichlorophosphazo Compounds from Nitriles. III. The Reaction between Acrylonitrile and PCl₃. The reaction of PCl₃ with acrylonitrile at higher temperatures gives CH₂Cl? CCl₂? CCl₂? N? PCl₃ ( II ). On pyrolysis of (II), CH₂Cl? CCl₂? CN (IV) is form- ed. Treatment of (II) with SO, results in CHzCL? CCl₂? CCl?N-P(0)Cl₂ ( III ). At lower temperatures and/or in the presence of PCl₃, acrylonitrile reacts with PCl₃ to give the cis/ trans isomers VIa and VIb .     

Crystal and molecular structure of tetrachlorophosphorus(V) hexachlorouranate(V)

The crystal structure of tetrachlorophosphorus(V) hexachlorouranate(V), PCl⁺₄.UCl^?₆, has been solved with 2492 independent F(hkl) collected by necessity from one component of a bicrystal; all crystals prepared were twinned. The structure is triclinic, space group P$\text{1}$, with a = 7.038(4), b = 7.373(4), c = 13.706(8) Å, α = 89.38(3), β = 88.80(3), γ = 105.20(3)°, with Z = 2. The two components of the bicrystal, in the volume ratio of 2.5 to 1, had their reciprocal lattice spots sufficiently separated to allow collection of the data set from component 1 with AgKα radiation (λ = 0.5608 Å). A model was derived from the Patterson synthesis and refined by least squares to R = Σ(|Fo|-|F_C|)/Σ|Fo| = 0.146. The structure was confirmed by a final (ρ_o-ρ_c) synthesis. The structure is an assembly of octahedral U(1)Cl^?₆, U(2)Cl^?₆ and tetrahedral PCl⁺₄ groups. The chlorine atom array is hexagonal close-packed, while the polyhedra are regular within the experimental errors. The structure is isomorphous with the transition metal analogues PCl₅.NbCl₅ and PCl₅.TaCl₅.     

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.     

Ramanspektroskopische Untersuchungen an PCl5 II. Das System PCl5—ZrCl4

Raman spectra of some solid and molten PCl₅–ZrCl₄ mixtures have been recorded. ZrCl₆ ^2– complex ions accompanied by at least one more chlorozirconate species are present in the solid as well as in the melt. The newRaman frequencies are attributed to ZrCl₅ ^–, which fundamentals are given and assignment is proposed to be analogous to TiCl₅ ^–. The presence of ZrCl₆ ^2– and ZrCl₅ ^– can be explained by the equilibrium ZrCl₆ ^2–+PCl₄ ⁺ZrCl₅ ^–+PCl₅.

     

Reaktionen des Trichlorphosphazophosphordichlorids,Cl3PN?PCl2

Reactions of Trichlorophosphazophosphorusdichloride, Cl₃P?N? PCl₂ P₂NCl₅ reacts with SbF₃ to give P₂NCl₃F₂ from which P₂NCl₄F is obtained by chlorination. Sulfur oxidizes P₂NCl₅ to yield SP₂NCl₅, SO₂ to yield SP₂NCl₅ and OP₂NCl₅. Reaction product from P₂NCl₅ and H₂S is SPCl₂(NH₂) besides PCl₃. P₂NCl₅ reacts with (n-C₄H₉)₃P to give (n-C₄H₉)₃P?N? PCl₂. All new compounds are characterized by their n.m.r. spectra and their chemical behaviour.     

NMR Study of the Interaction of Tin(II) and Antimony(III) Fluorides with Phosphorus Chlorides

Reactions of SnF₂ and SbF₃ with POCl₃ and PCl₅ in acetonitrile were studied by ¹⁹F, ³¹P, and ¹¹⁹Sn NMR. Tetrahedral compounds POF₂Cl and POF₃ form in the reaction with POCl₃. Interaction of SnF₂ and SbF₃ with PCl₅ yields higher (in terms of fluorine) octahedral complexes [PF₅ · MeCN] and [PF₆]^–. In all cases, fluorine-free phosphorus compounds are found in the acetonitrile solution.     

Synthesis of Dehydroabietic Chloride

The possibility of converting dehydroabietic acid into the chloride by treatment with SOCl₂, PCl₃, and PCl₅ was examined.     

Etude de la reaction de (MClcod)2 (M = Ir,Rh) avec les coordinats PClxPh3-x dans CDCl3

An NMR study of the reaction of (MClcod)₂ (M = Ir, Rh; cod = 1,5-cyclo-octadiene) with the ligands PCl_xPh_3-x, has been developed. Except when x = 3 we obtained as the first step the complex MClcod(PCl_xPh_3-x). This compound reacted with an excess of phosphine if x = 1 or 2, to give the complex MCl-(PCl_xPh_3-x)₃. However if M = Ir we have shown the formation of an intermediate species IrClcod(PCl_xPh_3-x)₂. We have studied the kinetics of the reaction:

When x = 3, we obtained the complexes (IrClcod)₂(PCl₃) and (IrClcod)₂(PCl₃)₃, for which we propose the structures.     

Synthesis and reactions of some substituted 1, 3, 5-triazines

The reactions of 2-substituted 4, 6-dihydroxytriazines with PCl₅ and SOCl₂ are investigated. It is shown that conversion of 2-(aryl- and substituted styryl)-4, 6-dihydroxy-1, 3, 5-triazine to the corresponding 4, 6-dichloro compounds is accompanied by ring opening and, in the case of styryl derivatives, by chlorination of the ethylene group. Analysis of the IR spectra of 4, 6-dihydroxytriazines establishes that under ordinary conditions they are 4, 6-dihydroxytetrahydrotriazines. Shift of the lactim-lactam equilibrium towards the oxo form is considered to be the reason why these compounds react with difficulty with SOCl₂. A mechanism for the reaction of triazine hydroxy derivatives with PCl₅ is put forward. New substituted triazines and intermediates are synthesized.     

Die Kristallstrukturen der Verbindungen PCl5NbCl5 und PCl5TaCl5

Crystals of PCl₅NbCl₅ and PCl₅TaCl₅ are isomorphous; space group P1 . The structures are ionic, consisting of tetrahedral cations PCl₄⁺ and octahedral anions NbCl₆^? and TaCl₆^?, respectively. Twinning is frequently observed in both compounds; an explanation thereof is given on the basis of the OD theorie.     

SPIROPHOSPHORANYLATION D'HYDROXYACIDES NATURELS (ACIDES MALIQUE,CITRIQUE ET TARTRIQUE)—EMETIQUES PHOSPHORES ET OLIGOMERES A PHOSPHORE PENTA ET HEXACOORDINE

Abstract

Condensing tartaric acid (R, R) and PCl₃, we obtained oligomers 3 and cyclic dimer 4. Oxidizing these compounds by DMSO, we prepared hydroxyphosphoranes 6–9, while reaction of orthoquinones gave six-coordinated compound 10. Compound 4 reacts with triethylamine leading to an equilibrium between phosphoranide 5 and phosphite 5'. The more likely structure of oligomers is a sequence of TBP arranged on a helix, whereas dimers should have an emetic structure with pentacoordinated phosphorus atoms. These results are supported by nmr analysis, molecular weight and elemental analysis. All these compounds have strong optical activity. On the other hand, condensing PCl₃ and malic or citric acids, we synthetized new functionalized spirophosphorans 2.

En condensant l'acide tartrique (R, R) et PCl₃, nous avons obtenu des oligomères 3 et le dimére cyclique 4. En oxydant ces composés par le DMSO, nous avons préparé les hydroxyphosphoranes 6–9, tandis que la réaction des orthoquinones a donné le composé a phosphore hexacoordiné 10. Le composé 4 réagit sur la triéthylamine, conduisant à un équilibre entre le phosphoranure 5 et le phosphite 5'. La structure la plus probable des oligomères est une série de BPT placées sur une hélice, tandis que les dimères devraient avoir une structure émétique avec les atomes de phosphore pentacoordinés. Ces résultats s'appuient sur l'analyse des spectres de RMN, les masses moléculaires et l'analyse élémentaire. Tous ces composés présentent une forte activité optique. Par ailleurs, en condensant PCl₃ et les acides malique ou citrique, nous avons synthétisé des spirophosphoranes fonctionnalisés nouveaux 2.     

Synthesis and Crystal Structure of (PCl4)[Re2Cl9]

The reaction between PCl₃ and ReCl₅ yielded at 200 °C the ionic tetrachlorophosphonium dirhenium nonachloride, (PCl₄)[Re₂Cl₉]. Single crystal X-ray diffraction analysis revealed a monoclinic unit cell: a = 8.616(3) Å, b = 10.449(4) Å, c = 9.397(3) Å, β = 99.72(3)°, V = 833.9(5) ų, Z = 2, sp. gr. P2₁/m, wR₂ = 0.1083 and R₁ = 0.0527. The ionic compound is built from tetrahedra PCl₄⁺ and face-sharing bioctahedra Re₂Cl₉^–. The Re–Re distance, 2.724 Å, indicates the presence of direct Re-Re interaction.