Reaction of oxophosphoranesulphenyl chlorides with phosphorus trichloride : A new synthesis of dialkyl phosphorochloridothionates and their optically active analogues

The reaction of acyclic oxophosphoranesulphenyl chlorides, with phosphorus trichloride has been found to give thiophosphoryl chlorides, and phosphoryl oxychloride—the products of the exclusive deoxygenation of sulphenyl chloride. Optically active phosphonochloridothionates and phosphorochloridothionates in a high state of optical purity have been obtained with inversion of configuration from optically active sulphenyl chlorides and phosphorus trichloride. It has been shown, however, that cyclic oxophosphoranesulphenyl chlorides undergo simultaneous desulphurisation and deoxygenation when treated with phosphorus trichloride. Using cis- and trans-isomers of 2-chlorothio-4-methyl-1,3,2-dioxaphosphorinan-2-one it has been demonstrated that deoxygenation is accompanied by inversion, whereas desulphurisation occurs with retention at phosphorus. The mechanism of the title reaction is discussed.     

One‐Pot,Four‐Component Reaction of Aryl Aldehydes,Aryl Ketones,Phosphorus Trichloride,and Acetonitrile Catalyzed by Acetyl Chloride: Synthesis of β‐Acetamido Ketones

The one‐pot, four‐component reaction of aryl aldehydes, aryl ketones, phosphorus trichloride, and acetonitrile, catalyzed by acetyl chloride, affords β‐acetamido ketones in good to excellent yields. Silicaphosphine (silphos), [P(Cl)_3‐n(SiO₂)_n], can also be used effectively as a solid‐supported reagent instead of phosphorus trichloride.     

A modified synthesis of 4-chloromethylthiazoles

A two-reaction synthesis of 2-substituted-4-chloromethylthiazoles from thioamides and 1,3-dichloroacetone is reported. The first step, cyclization to a 2-substituted-4-chloromethyl-4-hydroxythiazoline is carried out in the presence of bicarbonate in an aprotic solvent. Dehydration of this intermediate to a 2-substituted-4-chloromethylthiazole is accomplished by reaction with thionyl chloride, sulfuryl chloride, phosphoryl chloride, phosphorus trichloride or phosphorus pentachloride. Substituents on the thioamide, such as amino, alkyl, or aryl, are shown not to affect the success of the reaction. As a trend, alkylthioamides give slightly better yields of 4-chloromethylthiazoles than do arylthioamides. The yields of 4-chloromethylthiazoles prepared using this procedure are comparable to the yields obtained using acid catalyzed procedures.     

Halogen exchange reactions of silicon tetrafluoride with phosphorus trichloride and phosphoryl chloride

Silicon tetrafluoride undergoes halogen exchange reactions with both phosphorus trichloride and phosphoryl chloride at temperatures of 500–600°C yielding mixed chlorofluorides of silicon and phosphorus. It is interesting to note that, at these high temperatures, PCl₃ undergoes complete exchange to form PF₃ while POCl₃ reacts only with partial substitution, the major products being phosphorus chloride difluoride and silicon trichloride fluoride.     

Reactions of 2-oxo-2-dialkylamino-1,2-oxaphospholanes with acid chlorides

The reaction of acetyl chloride, chloroacetyl chloride, benzoyl chloride, and phosphorus trichloride with 2-oxo-2-dialkylamino-1,2-oxaphospholanes gives 2-oxo-2-chloro-1, 2-oxaphospholanes. Phosphorus pentachloride opens the 1,2-oxaphospholane ring with the formation of dimethylamido-3-chloroalkylphosphonyl chloride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1433–1434, June, 1990.     

SUBSTITUENT DIRECTIVE EFFECTS IN THE FRIEDEL-CRAFTS SYNTHESIS OF SUBSTITUTED PHENOXAPHOSPHINIC ACIDS

Abstract

Although meta-substituents on diphenyl ethers block attack at the para-position in the reaction with phosphorus trichloride and aluminium chloride, in some cases phosphorylation occurs in the even sterically more shielded ortho-position, leading to mixtures of isomeric phenoxaphosphinic acids. This effect and the obtained ratios of isomers can be explained by different substituent directive effects in a two step reaction mechanism.     

Nitrosyl isocyanate (ONNCO): gas-phase generation and a HeI photoelectron spectroscopy study

The nitrosyl isocyanate (ONNCO) has been generated from a heterogeneous reaction of gaseous nitrosyl chloride with silver isocyanate and studied for the first time in the gas phase. This structurally and energetically novel transient specimen is characterized by HeI photoelectron spectroscopy combined with DFT calculations. Both the calculations and the spectroscopic results suggest that the molecule adopts an open-chain trans structure. The observed decomposition products indicate the formation of ONNCO and further confirm the previously reported decomposition pathway.     

Some products of the reaction of phenylhydrazones and phosphorus trichloride

It is found that reaction of phosphorus trichloride with the phenylhydrazones of acetone, methylethyl, methylpropyl and methylbutyl ketones are compounds with one atom of phosphorus to one phenylhydrazone group. They do not contain chlorine, and distill without decomposition under vacuum. The view is advanced that they have structure I. A similar compound was also obtained by the reaction of phosphorus trichloride with acetaldehyde.     

Reaction of diethyl acetonedicarboxylate with nitrosyl chloride

The reaction of diethyl acetonedicarboxylate with greater than two equivalents of nitrosyl chloride or the reaction of diethyl isonitrosoacetonedicarboxylate with one equivalent of nitrosyl chloride gave diethyl 4-hydroxyisoxazole-3,5-dicarboxylate in quantitative yield. Mechanistic possibilities are discussed.     

An Unusual Synthesis of Arylazo Substituted Azaphospha [5, 1-A] Quinolines by Reaction of N-Alkylarylazo Quinolinium Salts with Phosphorus Trichloride

1,2-Dialkyl-3-arylazo quinolinium chloride 1 having N-methylene group activated by the insertion of arylazo site react with phosphorus trichloride to give N-(dichloro phosphinomethylene) quinolinium ylide 2 . The site of the reaction is determined by the relative activation of 1- and 2-methylene groups, in the absence of sufficient activation of N-methylene group, reactions occur at the 2-methylene group to give dichloro phosphinylated anhydrobases 5 and 11.     

Darstellung und isolierung isomerer phenoxaphosphinsäuren

In contrast to literature data, m-chloro, bromo or methyl substituents on diphenyl ethers do not block attack ortho to them in the reaction with phosphorus trichloride and aluminium chloride. By reacting diphenyl ethers 3 and 6 mixtures of the isomeric phenoxaphosphinic acids 4/5 and 7/8 were obtained, which were easily separated by crystallisation.     

Reactions of phosphorus halides with urethane

By the reaction of phosphorus trichloride, thiophosphoryl chloride, phosphorus oxychloride and phosphorus pentachloride with urethane in stoichiometric ratio 1:1 or 1:2 in benzene, compounds of the type

and

(X = S, O or Cl; n = 1 or 2) have been synthesized. A probable mechanism for their formation has also been suggested.     

A convenient preparative method for cyclic triphosphenium bromide and chloride salts

Analytically pure chloride and bromide salts of two different cyclic triphosphenium cations are prepared by the reaction of PX3 (X=Cl, Br) in the presence of the halogen-scavenging reagent cyclohexene. For the brominated species, the neutral, volatile 1,2-dibromocyclohexane byproduct is readily removed under reduced pressure, and the desired salts are obtained in high yield. Reactions involving phosphorus trichloride are complicated by the formation of salts containing both chloride and hydrogen dichloride anions. Reactivity experiments on potential undesired halogenated diphosphine byproducts suggest that the formation of such species can be prevented by increasing the concentration of cyclohexene employed in the reaction.     

Some chelating ion-exchange resins containing ketoiminocarboxyclic acids as functional groups

A series of ion-exchange resins containing -COCH(2)N[(CH(2))(m)COOH(2)](2) groups has been synthesized. Additional analogues were prepared by means of the reaction of the carbonyl group with phosphorus trichloride or thioglycollic acid. The properties of these resins and the selectivity for different metal ions have also been investigated.     

Reactions of heteroaryllithium compounds with phosphorus trichloride,phosphorus oxychloride,and thionyl chloride. Formation of heterocyclic biaryls

The reactions of four equivalents of heterocyclic aryllithium compounds with phosphorus trichloride or phosphorus oxychloride gave symmetrical heterocyclic biaryls in good yields. A similar coupling was found in the reactions of three equivalents of the lithium compounds with thionyl chloride.     

Aluminiumalkyle mit Heteroatomen. III. Über Reaktionen von Titan(IV)-chlorid mit Tris(trimethylsilylalkyl)-aluminium-Verbindungen

Aluminium Alkyls with Heteroatoms. III. On Reactions of Titanium(IV) Chloride with Trimethylsilylmethyl Aluminium Compounds Trimethylsilylmethyl titanium trichloride can be obtained by reaction of titanium(IV) chloride with tris(trimethylsilylmethyl)aluminium diethyl ether (1:1). Its catalytic activity for polymerisation of butadiene has been investigated.     

α‐Chlorination of Carboxylic Acids Using Trichloroisocyanuric Acid

Abstract

Carboxylic acids are chlorinated in the α position by heating with trichloroisocyanuric acid after formation of a small amount of the acid chloride using phosphorus trichloride.     

交联乙酰聚苯乙烯的合成及其膦化反应

交联聚苯乙烯在三氯化铝催化下与乙酸酐进行乙酰基化反应,得到交联聚苯乙烯乙酮树脂;研究了溶剂,温度,时间,试剂和催化剂用量对乙酰基化反应的影响。交联聚苯乙烯乙酮树脂进一步与三氯化磷作用,经冰醋酸处理,水解得到α-羟基膦酸树脂;溶剂,温度和时间对膦化反应均有影响。     

Simple method for the preparation of 1-oxo-1-chlorophospholenes

Conclusions A new and simple method has been found for the synthesis of 1-oxo-1-chlorophospholenes by the reaction of phosphorus trichloride, a diene, and an oxygen-donor compound, the best of which is acetone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1847–1848, August, 1972.     

2-isoxazolines from arylcyclopropanes: I. Monoarylcyclopropanes in a reaction with nitrosyl chloride activated by sulfur(IV) oxide

A reaction of monoarylcyclopropanes with nitrosyl chloride activated by sulfur (IV) oxide gave in good yields 5-arylisoxazolines. The reaction is of electrophilic character. A scheme of the reaction was suggested.