Phosphorus Halides Research Articles

Catalysis of the reaction of grignard reagents with silicon, tin, phosphorus, and arsenic halides and organohalides by copper salts with the formation of organic compounds of these elements

Catalysis of the reaction of grignard reagents with silicon, tin, phosphorus, and arsenic halides and organohalides by copper salts with the formation of organic compounds of these elements

Electric and Magnetic Anisotropy in Structural Organophosphorus Chemistry

Abstract The principles of study of the electric polarizability and magnetic susceptibility anisotropy of phosphorus derivatives have been discussed. The molar constants of birefringence in the transverse magnetic field (Cotton-frlouton constants, lo18 e.m.u.) have been determined for 2-methoxy-4-methyl-1,3,2-dioxaphosphorinane (-1.31, its 2-oxoanalogue (1.5), 2-thioanalogue (-16.3), phosphorus chloride (-112), phosphorus oxychloride (-87), and thiophosphoryl chloride (-12). The principal semiaxes of molecular magnetic susceptibility ellipsoids (1029 cm3) for the three latter compounds have been found equal: PCl3 k1 −9.90, k 2,3 −11.36; POCl3 kl −8.83, k 2,3 −11.28; PSCl3 k1 −13.28, k2,3, −13.17. The components of the magnetic susceptibility tensors of the phosphorus lone pair kL −2.15, kt −2.32 and of the bonds P-0 kL −4.35, kT −2.23; P-Cl kL −4.17, kT −2.05; P→O kL −1.11, kT −0.44; P→S kL −4.17, kT −2.17 have been calculated using data on the magnetic anisotropy effects on chemical shifts in PYR spectra of dioxaphosphorinanes. The relationship between the mean values of the magnetic susceptibility and electric polarizability phosphorus derivatives has been established, k = −0.060–1.046.10−5 b. The magnetic anisotropies of bonds have been shown to depend on their environment, for phosphoryl on the Kabachnik constants of substituents at the phosphorus atom.

Studies on Organophosphorus Compounds; XLI. A Convenient Synthesis of Alkyl Hydrogen α-(Benzyloxycarbonylamino)benzylphosphonates

Alkyl hydrogen α-(benzyloxycarbonylamino)benzylphosphonates are prepared from substituted benzaldehydes, benzyl carbamate, and phosphorus(III) chloride in acetic acid containing thionyl chloride and subsequent alcoholysis. The reactions proceed smoothly at room temperature and afford the title compounds in moderate to good yield.

Reactions and Rearangements of Carboxamides Phosphorylated by Tervalent Phosphorus Chlorides

Reactions and Rearangements of Carboxamides Phosphorylated by Tervalent Phosphorus Chlorides

ChemInform Abstract: Comments on the Synthesis of Aminomethylphosphonic Acid.

Two simple methods for the synthesis of aminomethylphosphonic acid from phosphorus (III) chloride and 1,3,5-triacylhexahydro-1,3,5-triazine or N-(hydroxymethyl) benzamide are described

ChemInform Abstract: The Reaction Between N‐Methyl‐p‐toluohydroxamic Acid and Tervalent Phosphorus Compounds: A Thermal PIII → PV Rearrangement Proceeding by a Radical Mechanism.

AbstractThe hydroxamic acid (I) reacts with various chlorides of phosphorus(III) in the presence of Py at ‐60 °C to give the P(III) intermediates (III).

ChemInform Abstract: o‐Phosphorylated Phenols and Their Methoxymethyl Ethers, Phosphines, and Phosphine Oxides.

AbstractThe phenol ether (III) reacts after lithiation with the phosphorus chlorides (IV) and (VI) to give the phosphines (V) and the phosphine oxides (VII).

ChemInform Abstract: Methylene Compounds of Non‐Metals. Part 7. Preparation and Reactions of Methylthiomethyl Substituted Phosphorus Halides.

ChemInform Abstract: Methylene Compounds of Non‐Metals. Part 7. Preparation and Reactions of Methylthiomethyl Substituted Phosphorus Halides.

ChemInform Abstract: Oxidation of Phosphorus(III) Halides by Red Photolysis of Ozone Complexes in Solid Argon.

AbstractThe phosphorus halides PX3 (X: F, Cl, Br) all form molecular complexes with ozone in solid argon.

ChemInform Abstract: N‐ and C‐Phosphorus(III)‐Substituted Azomethine Derivatives and Their Rearrangements.

AbstractReaction of the phosphorus(III) halides (I), (IV), (VII), or (XI) with the azomethines (II) or (VI) gives the N‐phosphorylated enamines (III) or (VIII), the diazaphospholes (V), or the C‐phosphorylated azomethine (Xb) depending on the starting materials.

ChemInform Abstract: Prototropic Phosphoryl ‐ Hydroxy Ylide Tautomerism. Part 3. Influence of the Substituents at the Phosphorus Atom on the Tautomeric Equilibrium of Tosyl‐Substituted (Phosphorylmethyl)triphenylphosphonium Salts.

AbstractReaction of the phosphorus(III) chlorides (I) with the tosylmethylphosphonium salts (II) and subsequent oxidation give the phosphoranes (III) which are converted to the phosphonium salts (IV).

Synthèse du 5-bromométhyl- et du 5-chlorométhyl-2-furannecarboxaldéhyde

The action of hydrogen halides, sulfur and phosphorus halides, and halotrimethylsilanes on 5-(hydroxymethyl)-2-furancarboxaldehyde ( 1) led to the corresponding 5-(chloromethyl)- ( 2) or 5-(bromomethyl)-2-furancarboxaldehyde ( 3). Thus, treatment of 1 in diethyl ether solution with gaseous dry hydrogen chloride under very mild experimental conditions led to high yields of 2. The selective and quantitative conversion of 1 into 3 was achieved with bromotrimethylsilane. In the same manner, chlorotrimethylsilane gave high yields of 2 from 1. The latter compound was obtained by acid-catalyzed dehydration of d-fructose in dimethyl sulfoxide, and then converted into 2 without prior purification.

Oxidation of phosphorus(III) halides by red photolysis of ozone complexes in solid argon

PCl{sub 3}-O{sub 3} and PBr{sub 3}-O{sub 3} complexes in solid argon photolyze to give phosphoryl halides with red visible radiation that has no effect on isolated ozone. These observations and similar results for PH{sub 3}-O{sub 3} and P{sub 4}-O{sub 3} complexes show that the complex markedly increases the cross section for red photodissociation of ozone and suggest that this increase is due to the complex effectively lowering the barrier to dissociation by providing a strongly exothermic dissociation-recombination process.

Mechanisms of Formation of the Cyclodiphosphazane and Cyclotriphosphazane Ring Systems

Abstract Four- and six-membered phosphorus(V) nitrogen ring compounds have been prepared from phosphorus(V) halides and amides, and their structures determined by n.m.r, mass spectroscopy and X-ray crystallography. The role of three-coordinated intermediates is discussed.

Comments on the Synthesis of Aminomethylphosphonic Acid

Two simple methods for the synthesis of aminomethylphosphonic acid from phosphorus (III) chloride and 1,3,5-triacylhexahydro-1,3,5-triazine or N-(hydroxymethyl) benzamide are described

ChemInform Abstract: Transition‐Metal Phosphinidene Complexes: Syntheses, Structures, and Bonding in Dinuclear Phosphinidene Complexes Containing 14‐ and 15‐Electron Metal Fragments.

AbstractThe reaction of the phosphorus chloride (I) with (II) produces the dicobalt‐phosphinidene complex (III), which is characterized by X‐ray crystallography (space group Cmcm, Z=4).

Quantum-chemical study of donor-acceptor interactions between silicon, phosphorus, and sulfur halides and ammonia

1. Donor-acceptor interactions between silicon, phosphorus, and sulfur halides and the nitrogen atom in the ammonia molecule were studied theoretically by applying the LCAO-MO method in the MNDO approximation. 2. According to the calculation, an approximation of a supermolecule with a complete optimization of geometry shows that the strength of the donor-acceptor bond in complexes with NH3 decreases in the series PCl3 > SiF4 > SiCl4 > SCl2 > PF3 > SF2, while heat of the formation and charge transfer are higher in complexes of silicon, phosphorus, and sulfur halides with ammonia molecules than in the corresponding complexes with formaldehyde.

ChemInform Abstract: Reaction of Bulky Monosubstituted Phosphorus(III) Halides with Disodium Pentacarbonylchromate. Steric and Electronic Factors in the Synthesis of Cr(CO)5 Complexes of Diphosphenes, Phosphinidenes, Phosphanes, Diphosphanes, and Cyclopolyphosphanes.

AbstractThe title reactions lead to at least nine different types of products (depending on the size and electronic properties of the substituent on P) as to be seen from the scheme.

ChemInform Abstract: Reaction of Bulky Monosubstituted Phosphorus(III) Halides with Disodium Tetracarbonylferrate. Steric and Electronic Factors in the Synthesis of Fe(CO)4 Complexes of Diphosphene and Phosphinidene Ligands.

AbstractThe products of the title reactions (see scheme), depending on the substituent at P, are compared with those from analogous reactions using Na2Cr(CO)5.

SYNTHESIS OF SOME PHOSPHORUS DERIVATIVES OF CARDANOL

Abstract The synthesis of some phosphonates obtained by reaction of cardanol and 3-n-pentadecylphenol with pentavalent phosphorus chlorides containing oxygen or sulfur atom is reported.