Reaction Of Phosphorus Pentachloride Research Articles

Synthesis, Characterization, and Thermal Degradation Property of Aniline Polyphosphazene

Aniline polyphosphazene was successfully prepared through the following three steps, which were characterized by Fourier transform infrared (FT-IR), 1H-nuclear magnetic resonance (NMR), and 31P-NMR. The first step was the synthesis of hexachlorocyclotriphosphazene through the reaction of phosphorus pentachloride and ammonium chloride; the second step was the preparation of polyphosphazene by thermally initiated ring-opening polymerization of hexachlorocyclotriphosphazene; the third step was the preparation of aniline polyphosphazene by the reaction of aniline and polyphosphazene. The results of Thermogravimetry-Mass Spectrograph (TG-MS). under pure argon atmosphere indicated aniline polyphosphazene began to decompose at about 280°C and had a char yield of 41% at 920°C; some of the side chains first break from its main chain with the release of aniline from 280°C and some break at about 500°C with the release of benzene groups; finally the main chain of aniline polyphosphazene and the fragments of C6H6 or C6H5-NH2 began to break at 800°C with the release of CN−, N2 and C2H4.

Reactions of bicyclo[4,1,0]heptane derivatives with phosphorus pentachloride

Bicycloalkanes containing three-membered cycle possess the enhanced activity to electrophile reagents action due to raised angular and torsion strains. In this connection the study of reactions of phosphorus pentachloride with bicyclo[4,1,0]heptane derivatives are of significant interest. We pioneered in using as a latter the easily available norcarane, 7,7-dichloroand 2-alkoxy-7,7-dichloronorcaranes Ia–Ic. Under standard conditions [1], norcarane was found to phosphorylation with a small ring cleavage to form cyclohexylidenemethyland 1-chlorocyclohexylmethylphosphonic dichlorides. 7,7-Dichloronorcarane does not react with phosphorus pentachloride under similar conditions that is probably caused by the increased small ring stability. 2-Alkoxy-7,7-dichloronorcaranes Ia–Ic are phosphorylated on alkoxyl group to give 2-(7,7dichlorobicyclo[4,1,0]heptyl-2-oxy)ethenylphosphonic dichlorides IIa–IIc. Theoretically possible reaction pathway at the cycle is not observed that is proved by the absence of product with P–C bond when one carried out reaction with 2-methoxy-7,7-dichloronorcarane. This reaction gives rise only to 3-dichloromethylenecyclohexanone, the product of competitive reaction occurring at the three-membered cycle. The possible scheme of the formation of latter was described by us earlier [2]. DOI: 10.1134/S1070363210050336

Reaction of phosphorus pentachloride with N-vinylimidazole and N-vinylbenzimidazole

Earlier, we have found that N-vinylpyrazoles are phosphorylated with phosphorus pentachloride at the double bond to give rise to unsaturated organophosphorus compounds [1]. N-Vinylimidazoles contain-ing in the ring highly basic separated nitrogen atoms of the pyridine type react with phosphorus pentachloride in a different manner. In these reactions, the first and foremost are the donor–acceptor interactions. N-Vinylimidazole I reacts with phosphorus pentachloride (even in the excess of the latter) to give the donor– acceptor complex III with participation of the pyridinium nitrogen atom. As a result, the electron–acceptor properties of the ring increase and the nucleophilicity of the N-vinyl group decreases hampering its phosphorylation. The treatment of azole I with the solution of phosphorus pentachloride in benzene saturated with hydrogen chloride affords complex compound IV containing the protonated nitrogen atom in the 3 position.

Phosphorylation of C-alkenylsubstituted pyrazoles with phosphorus pentachloride

The reaction of phosphorus pentachloride with styrenes affords unsaturated organophosphorus compounds in which the phosphorus chloride substituent is attached to the carbon atom of the double bond [1]. NVinylsubstituted azoles are also phosphorylated at the double bond [2–3]. Phosphorylation of С-alkenylazoles with phosphorus pentachloride was not studied until now. The presence in the azole cycles the “pyridine” nitrogen atoms with enhanced nucleophilicity could direct the attack of phosphorus pentachloride to the heterocycle rather than to the double bond of Сvinylazoles to give donor–acceptor complexes. Indeed, the reaction of phosphorus pentachloride with 1-allyl3,5-dimethylpyrazole led to formation of the donor– acceptor complex I. DOI: 10.1134/S1070363209060358

2-[Dichloro(phenoxy)methyl]phenyl dichlorophosphonate

The reaction of phosphorus pentachloride with phenyl salicyl­ate yielded a compound of chemical formula C13H9Cl4O3P, which was originally thought to contain a P—O—C heterocycle. The true molecular structure has now been established by the determination of its crystal structure. There are two molecules in the asymmetric unit.

Reaction of 1,2‐trans‐Glycosyl Acetates with Phosphorus Pentachloride: New Efficient Approach to 1,2‐trans‐Glycosyl Chlorides.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Reaction of 1,2- trans-glycosyl acetates with phosphorus pentachloride: new efficient approach to 1,2- trans-glycosyl chlorides

Reaction of phosphorus pentachloride with 1,2- trans-glycosyl esters is described. The reaction mechanism presumably involves formation of a tetrachlorophosphonium ion as one of the key reactive intermediates, which can be induced either by Lewis acids or by using acetonitrile as the reaction solvent. Two novel, efficient methods for the synthesis of the thermodynamically unstable glycosyl chlorides were developed based on this reaction.

Regiochemistry of the reaction of 3,6-bis(tert-butyl))-1,2-benzoquinone with phosphorus trichloride in the presence of arylacetylene

The reaction of phosphorus pentachloride with arylacetylenes followed by hydrolysis of the initially formed phosphonium products is considered as an important method for the synthesis of derivatives of unsaturated phosphonium acids which can be used as initial compounds to prepare various types of new promising biologically active organophosphorus products [1]. The replacement of two chlorine atoms in phosphorus pentachloride by the phenylenedioxy fragment results unexpectedly in 2,6-dichloro-2oxobenzo[ e ]-1,2-oxaphosphorines, which are products of multistep transformations including easy formation of the P‐C bond and the phosphoryl group, ipso -substitution of the oxygen atom, and regioselective chlorination of the aromatic ring in the para -position relative to endocyclic oxygen of the phosphorine heterocycle [2‐ 4]. A similar synthetic outcome can be attained in the phenanthrenequinone‐phosphorus trichloride‐arylacetylene ternary system, in which isolation of the

Novel Route to β-Chloro Vinyl Sulfonesviathe Action of Phosphorus Pentachloride on Phenacyl Aryl Sulfones in Chloroform

Abstract Since our interest is in studying the kinetics and mechanisms of nucleophilic substitution and elimination reactions of halo olefins1–3 so the aim of this work is to prepare compounds of the type C6H5CCI=CHSO2 and to study their behaviour towards elimination and substitution reactions. Earlier preparation of these sulfones by thermal or copper-catalyzed addition of aryl sulfonyl bromides and chlorides to phenylacetylene reported a mixture of E- and Z- β-halovinyl sulfones or exclusively E-isomer4–7. The reaction of phosphorus pentachloride with phenacyl aryl sulfones is investigated as a possible route to prepare β-chlorovinyl sulfones.

Electrophilic 3,5-Substitution of 2,4,4,6-Tetraphenyl-4H-pyran and Some of Its 1-Heteroanalogues

The reaction of dibromine with the heterocycles I-IV gives corresponding 3,5-dibromo derivatives, while the less selective reactions with dichlorine afforded 3,5-dichloro derivative XII only in the case of 4H-thiopyran IV and trichloro derivative of the probable formula XIII in the case of 1,4-dihydropyridine II. Dichloro derivative IX was obtained on reaction of phosphorus pentachloride with substrate I. Nitration of compounds I-IV gives 3,5-dinitroderivatives XV-XVIII, but mononitro derivatives XIX and XX were also obtained. Iodination of compounds II-IV with di-iodine was unsuccessful.

Reactions of phosphorus pentachloride with N,N'-dialkyl- and N-alkyl-N'-acetylureas

N,N′-dialkylureas are phosphorylated by phosphorus pentachloride to give cyclic trichlorodiazaphosphetidinones. The formation of these derivatives in the reaction of N-methyl-N' -chloroacetylurea with PCl5 is accompanied by the chlorination of the N-acetyl fragment.

ChemInform Abstract: Reaction of Phosphorus Pentachloride with Perhalocarbonyl‐Containing Compounds.

AbstractThe polyfluorinated ketones (III) or diketones (VI), prepared by coupling the esters (II) or diesters (V) with the perfluoroalkyl iodides (I) or (IV) in the presence of methyllithium, are heated with phosphorus pentachloride to form the chlorinated products (VII) ‐ (IX).

The unusual course of the reactions of phosphorus pentachloride with 1-phosphorylated alcohols and acetals

The unusual course of the reactions of phosphorus pentachloride with 1-phosphorylated alcohols and acetals

ChemInform Abstract: Reaction of Phosphorus Pentachloride with 2‐Chloroheptylphosphonic Dichloride in Benzene and Subsequent Treatment of the Reaction Mixture with Arsenic Trifluoride.

ChemInform Abstract: Reaction of Phosphorus Pentachloride with 2‐Chloroheptylphosphonic Dichloride in Benzene and Subsequent Treatment of the Reaction Mixture with Arsenic Trifluoride.

ChemInform Abstract: Reaction of Phosphorus Pentachloride with Cyclohexenyl Esters of Carboxylic Acids.

AbstractThe esters (I) react with PCl5 to give the chlorinated derivatives (II).

ChemInform Abstract: On the Reaction of Phosphorus Pentachloride with αβ‐Unsaturated Carbonyl Compounds.

AbstractThe αβ‐unsaturated carbonyl compounds (I) are combined with phosphorus pentachloride and subsequently with sulfur dioxide to give the vinyl dichlorophosphates (II).

ChemInform Abstract: Reaction of Phosphorus Pentachloride with Mixtures of a Trialkylphosphite and an Aldehyde.

AbstractReaction of phosphorus pentachloride (I) with the phosphites (II) and acetaldehyde (III) produces mixtures of the dialkylchlorophosphates (IV) and the dialkylphosphoryl ethyldichlorophosphites (V).

ChemInform Abstract: On the Reaction of Phosphorus Pentachloride 1‐Alkene Adducts with Arsenic Trifluoride.

AbstractDas Additionsprodukt von Phosphorpentachlorid an die Alkene (I) reagiert in Benzol in Gegenwart von Arsentrifluorid nach Art einer Friedel‐Crafts‐Alkylierung je nach Temperatur zu den Alkylbenzolen (III) sowie dem Alkenylphosphortetra?uorid (II) oder den AIkylphosphonsäuredifluoriden (IV).

Reaction of phosphorus pentachloride with 2-acetylthiophene and acetophenone

Reaction of phosphorus pentachloride with 2-acetylthiophene and acetophenone

REACTION OFo-BENZENEDITHIOLS AND DERIVATIVES WITH PHOSPHORUS PENTACHLORIDE

Abstract Reaction of phosphorus pentachloride with thiocatechol, 4-methyl-1,2-benzenedithiol and their trimethyl-silylated derivatives under a variety of conditions produced chlorodithiophosphites in which a 5-membered ring with two sulfurs is bonded to phosphorus. The other product of this reaction is probably an oligomeric disulfide derived from the original dithiol.