Phosphorus heterocycle synthesis using RPX2·AlX3 addition to 1,4-dienes—1

A new synthetic sequence of phosphorus heterocycles was developed using RPX₂·AlX₃ complex addition to 1,4-dienes. For example, the reactions of PhPX₂ (X=Cl, Br), CH₃PCl₂ and PCl₃AlCl₃ complexes with 1-allyl-cyclohex-1-ene to give two isomeric 2-phosphatricyclo [4.4.0.0^4,6] decanes (i.e.2 and4) accompanied by a phosphorus acid chloride (3) are described. Several transformations of2 into other ring systems, namely phosphadecaline and perhydrophosphindoline are mentioned.     

Darstellung,Kristall- und Molekülstruktur von Triphenylphosphinoxidhydrochlorid (C6H5)3PO · HCl

On Phosphazo Compounds from Nitriles. IV. The Reaction of Tri, Di, and Monochloroacetonitrile with [Cl₃P?N? PCl₃]Cl. Improved Preparation of [Cl₃P?N? PCl₃]Cl Trichloroacetonitrile reacts with P₂NCl₇ to give Cl₃C? CCl₂? N?PCl₂? N?PCl₃ I , dichloroacetonitrile to give Cl₂C?CCl? N?PCl₂? N?PCl₃ II , and chloroacetonitrile to give the ring compound III . Preparation, n.m.r. and mass spectra of the new compounds are described. The mechanism of formation is discussed. An improved procedure for the preparation of P₂NCl₇ is given.     

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 .     

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.     

Synthese und Eigenschaften linearer Phosphorylchlorphosphazene

Synthesis and Properties of Lineary Phosphorylchlorphosphazenes The phosphorylchlorphosphazenes, Cl₂(O)P—[N?PCl₂]_n—Cl, (n = 1, 2, 3) react like POCl₃ with hexamethyldisilazan forming silylamides, Cl₂(O)P—[N ? PCl₂]_n—NHSi(CH₃)₃, (n = 0, 1, 2, 3). From these are obtained the phosphorylchlorphosphazenes by reaction with PCl₅ containing one group —N ? PCl₂ more.     

Gasphasen-Reaktionen. 92. Thermische HCl-Abspaltung aus Alkyldichlorphosphanen (H3C/H)3C?PCl2 zu Phosphaalkenen (H3C/H)2CPCl und Phosphaalkinen (H3C/H)C≡P

Gasphase Reactions. 92 Thermal Elimination of HCl from Alkyldichlorophosphanes (H₃C/H)₃C? PCl₂ to Phosphaalkenes (H₃C/H)₂C?PCl and Phosphaalkines (H₃C/H)C≡P The alkyldichlorophosphanes H₃C? PCl₂, ClH₂? PCl₂, (H₃C)H₂C? PCl₂ and (H₃C)₂HC? PCl₂ split off HCl on heating in a gasflow under reduced pressure. PE spectroscopic gas analysis proves that under these conditions the short-lived phosphaalkenes H₂C?PCl, (H₃C)H₂C?PCl and – catalyzed by [MgCl₂? MgO/SiO₂]_∞ – (H₃C)₂C?PCl as well as the phosphaalkines HC≡P and (H₃C)C≡P are formed, all of which can be isolated by low temperature condensation. Based on the PES ionization patterns recorded and on the MNDO calculations for their assignment, the π_CP multiple bonds are discussed. The presumable pathway of the HCl elimination is rationalized for (H₃C)H₂C? PCl₂ by an approximate MNDO energy hypersurface.     

Alternative Synthesis of A C,C-Diacetylenic Phosphaalkene

Abstract

Bis(trimethylsilyl)-terminated C,C-diacetylenic phosphaalkene was prepared from Mes*PCl₂ and a propargylic Grignard reagent that in turn was formed from 3-bromo-1,5-bis(trimethylsilyl)penta-1,4-diyne and Rieke-Mg.     

Preparation,Reactions, and NMR Studies of 4-Methyl-4-Phospha-Tetracyclo [3.3.0.02,8.03,8] Octane 4-Oxide and Derivatives

Abstract

The title compound which we¹ and others² have previously synthesized has now been extensively investigated. The tetracyclic phosphonium chloride 1 was prepared by treatment of norbornadiene with CH₃PCl₂ at 65–80°C for one week. Treatment of 1 with AICl₃/CH₂CI₂ gave 2. Direct or “Inverse” addition at water to 2 dictated the stereochemistry of the oxide 3. Stereoassignments of 3 were made based on lanthanide shift ?¹H and ¹³C nmr studies studies. Extensive 2-D nmr studies (HETCOR, COSY) and triple irradiation experiments enabled chemical shift and coupling constant assignments.     

Organophosphorus Synthesis Without Phosphorus Trichloride: The Case for the Hypophosphorous Pathway

Abstract

The vast majority of organophosphorus compounds is currently synthesized from phosphorus trichloride (PCl₃), even though the final consumer products do not contain reactive phosphorus–chlorine bonds. In order to bypass phosphorus trichloride, significant interest has been devoted to functionalizing elemental phosphorus (P₄, the precursor to PCl₃), red phosphorus (P_red), or phosphine (PH₃). Yet, other industrial-scale precursors are hypophosphorous derivatives (H₃PO₂ and its alkali salts), but their use as phosphorus trichloride replacements has been completely overlooked. Here, the case is made for an alternative approach to the industrial synthesis of organophosphorus compounds based on hypophosphites.     

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.     

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.     

Elucidation of the Reaction Products of Acetonitrile with Phosphorus Pentachloride

Abstract

The reaction of acetonitrile with PCl, results in the ionic compounds (1) to (4) containing the trichloro[2-chloro-2-[(trichlorophosphoranyli-dene)amino]ethenyl]phosphorus cations and not in the compounds [CH2?C?NPCl₃]PCl₆1 or trichloro[2-chloro-1 -[(trichlorophosphoranyli-dene)amino] ethenyl]phosphorus hexachlorophosphate (5) as assumed from ³¹P-NMR spectra [2, 3]. The crystal structures of the compounds (1) to (4) were determined with X-rays at 95K. As observed for the CI-C(NPCl₃); cation all the cations show cis-trans conformations with respect to their CI-C-X-P torsion angles. The wcl3 groups of the cations have two different orientations with one C?N?P?CI torsion angle of about 0° (cis) as in (1) or about 180° (trans) as in (3) and (4). In the salt (2) there are two formula units in the asymmetric unit with one cation showing the cis and the other showing the tram conformation.     

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.     

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 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.     

SOME PHOSPHORYLATED DERIVATIVES OF 1- AND 2-ADAMANTANOLS AND 1-ADAMANTYLAMINE

Abstract

The phosphorylation of 1- and 2-adamantanols and of 1-adamantylamine with POCl₃, PSCl₃, PhOP(O)Cl₂, 4-ClC₆H₄OP(O)Cl₂, and PCl₃ is described and the conversion of the obtained phosphorochloridates into a number of derivatives such as phenylhydrazides, diamidates, hydrazides, hydrazones and azides is reported.     

Dichlorophosphate zweiwertiger Übergangsmetalle von Mangan,Eisen, Kobalt,Nickel und Kupfer

Dichlorophosphates of the Divalent Transition Metals Manganese, Iron, Cobalt, Nickel, and Copper The dichlorophosphates M(O₂PCl₂)₂ · 2 POCl₃ with M = Mn, Fe, Ni and Co(O₂PCl₂)₂ are prepared from the metal acetates and POCl₃, whereas Cu(O₂PCl₂)₂ only yields from the formiate and P₂O₃Cl₄. The finely distributed metals Fe, Co, and Ni react with excess dichlorophosphoric acid. forming the complexes M(O₂PCl₂)₂ · 2 HOPOCl₂. According to the vibrational spectra, the metal atoms are linked to polymeric 8-ring structures by O? P? O bridges. Moreover the dichlorophosphoric acid solvates are stabilized by hydrogen bridges.     

Synthesis,Structural, and Physicochemical Study of First- and Second-Generation Melamine-Based Dendrimers

Abstract

First-tier (G₁) 2,4,6-tridiethymalonate-triazine (2,4,6-TDEMTA) and second-tier (G₂) 2,4,6-hexadiethylmalonate-triazine (2,4,6-HDEMTA) dendrimers were prepared with melamine (1,3,5-triazine) as core (G₀) and sodium malonate ester for bifurcation of chains. The trichlorotriazine (TCT) and sodium diethyl malonate (SDEM) aqueous solutions were mixed, and a creamy white precipitate of G₁ was obtained. The G₁ was hydrolyzed in alkaline medium to prepare 2,4,6-tridisodiummalonate-triazine (2,4,6-TDSMTA) by replacing ?C₂H₅ groups of COOC₂H₅ by Na, which was further neutralized by dilute HCl to obtain 2,4,6-trimalonicacid-triazine (2,4,6-TMATA). The TMATA was treated with PCl₅(s) to form –COCl, which was treated with SDEM to form the G₂.     

Homologe Alkyliminophosphorsäuretrichloride und deren Ammonolyse

Aus PCl₅ und aliphatischen primärenn-Aminen werden dimere Alkyliminophosphorsäuretrichloride (n-RN=PCl₃)₂ erhalten. Mit aliphatischen primäreni-Aminen entstehen entweder monomere oder dimere Verbindungen der Formel (i-RN=PCl₃) _n (n=1,2) je nach der Basenstärke des eingesetzten Amins und je nach dem Ort der Verzweigung zum Stickstoffatom des Amins. Die Verbindungen reagieren mit wasserfr. NH₃ in exothermer Reaktion zu Alkyliminophosphoniumsalzen [RNH–P(NH₂)₂]₂ N⁺Cl^–. Die IR-,¹H- und³¹P-NMR-Spektren der Verbindungen werden mitgeteilt.Phosphorus(V)chloride reacts with primaryn-alkylamines to dimeric phosphazenes (n-RN=PCl₃)₂. The analogous reaction with primaryi-alkylamines leads either to monomeric or dimeric compounds (i-RN=PCl₃) _n (n=1,2), depending on both the basicity of the reacting amine and from the place of branching relative to the nitrogen atom of the amine. Ammonolysis of these phosphazenes leads to 1,1,3-triamido-1,3-dialkylimino-4,4-dihydridoketadiphosphonitrilium^* chlorides [RNH–P(NH₂)₂]₂ N⁺Cl^–; IR-,¹H- and³¹P-NMR-spectra are reported.

---

---

Nomenklatur analog zuF. G. Sherif undC. D. Schmulbach, Inorg. Chem.5, 322 (1966).