Chlorides of phosphorus

The hydriodic acid is then decomposed by chloiine, and ICl regenerated. Phosphorus acts by for.ming the chloride of phosphorus from which the acid chloride is produced, which is more readily attacked by chlorine than the acid. Sulphur behaves in a similar fashion, sulphur chloride converting the... 

The course of the reaction is similar when the chlorides of phosphorus (or phosgene) are used. 

With the chlorides of phosphorus there is an interchange of halogens, thus—... 

The at. refraction is least in the chlorides of phosphorus and greatest in the iodide,... 

A convenient method for the production of phosphorus-containing indoles with P-O-C bond may be the reaction of hydroxyindoles with the chlorides of phosphorus acids [59, 60, 158], 5-Hydroxyindole, obtained by the Nenitzescu reaction [160, 161], and amidophosphite (toluene, 110°C) form the unstable 5-phosphitoindoles 62 (132-124 ppm), which are isolated in the form of thiophosphates 63 (62-64 ppm) [159] ... 

A. N. Pudovik u. V. K. Khairullin, Reaction of the Chlorides of Phosphorus Acids with Unsaturated Compounds, Usp. Khim. 37, 745 (1968) engl. 317. 

A double chloride of phosphorus and iron, FeCl3.PCl5, has been isolated 10 by acting on ferric oxide with phosphorus pentachloride. It also results on direct union of the two chlorides. 

SYNS CHLORIDE of PHOSPHORUS FOSFORO-(TRICLORURO di) (ITALIAN) FOSFORTRICHLORIDE PUTCH) PHOSPHORE(TRICHLORURE de) (FRENCH) PHOSPHORTRICHLORID (GERMAN) PHOSPHORUS CHLORIDE TROJCHLOREK FOSFORU (POLISH)... 

When the other chloride of phosphorus, phosphorus penta-chloride PCI5 reacts with water a reaction takes place, in which it is probable that two chlorine atoms from the penta-chloride exchange places with the oxygen of the water, two molecules of hydrochloric acid being thus formed. 

Sulphon Chlorides.—(2) Reaction with phosphorus penta-chloride. As sulphonic acids contain the acid hydroxyl group, they undergo the characteristic reaction with chlorides of phosphorus and exchange the hydroxyl for chlorine. The product is known as a sulphon chloride. 

Practically, the above reactions are combined into one operation. The above condensation-product is treated with a chloride of phosphorus or phosgene, and the resulting chloride,... 

With respect to the properties of chlorobenzoyl we have yet to remark that by warmth it dissolves phosphorus and sulphur, which by cooling again separate in the crystalline form. With sulphuret of carbon, it may be mingled in every proportion, and, as it would seem, without suffering decomposition. With solid chloride of phosphorus, it becomes strongly heated, with the formation of liquid chloride of phosphorus and an oily, strongly smelling body which we have not farther examined. 

Such a decomposition probably occurs in the case of all substances belonging to the NH3+HGI type at least the vapor density of ammonium chloride, of phosphorus pentachloride, etc. suggest that these bodies do not vaporize without decomposition, that their vapor in fact is a mixture of two vapors, which recombine when the temperature is lowered, as has been demonstrated with certainty in the case, for instance, of tetraethyl ammonium iodide. [The same view is expressed in the March issue of the Armalen, 105, 390 ff, the present article of Kekuld reached the editors after the closing of that issue but before its publication.— D.R.]... 

This reaction is without practical importance, since the reactions involved in the methods described under (2), page 116, take place much more smoothly and easily, and, therefore, are exdusively used. The above reaction is mentioned here only because it throws some light on one of the methods used in esterification, which will be briefly described below under the characteristics of the acid-chlorides. In practice, the add-chlorides are almost always prepared by the action of phosphorus tri- or penta-chloride on the add directly, or in many cases, on the sodium or potassium salt. Phosphorus oxychloride is employed in rare cases. The selection of the chloride of phosphorus depends upon... 

Lesson 3 -Reactions of chlorides of phosphorus with water. -Students were required to construct a concept map about the reactions of chlorides of phosphorus with water through self-study. 

Table 17. PCI bond distances in acyl chlorides of phosphorus, phosphonic and phosphoric acids...

The action of the chlorides of these elements still further illustrates the progressive change in their chemical properties. The complete hydrolysis of the chlorides of phosphorus has already been observed. Arsenious chloride becomes hydrolyzed to a very great extent although some arsenious ions still exist in solution, as was stated above. Antimony chloride forms an oxychloride and bismuth chloride a basic chloride when these compounds are added to water. These facts indicate partial hydrolysis in both cases. 

Sulfuryl chloride can be employed in conjunction with numerous chlorine carriers to effect substitution in either the ring or side chain. The chlorides of antimony, iron, molybdenum, and aluminum are valuable with sulfuryl chloride in effecting substitution in the ring. The chlorides of phosphorus and, to a lesser extent, manganese, arsenic, and bromine favor side-chain substitution. Sulfur accelerates both types of substitution. 

The chlorides of phosphorus replace the hydroxyl group in acetic acid by chlorine. The replacement is an example of a general reaction which has been mentioned in connection with the alcohols. The equation for the reaction (274) in the case of phosphorus trichloride is as follows —... 

In the technical preparation of acetyl chloride sulphuryl chloride, SO2CI2, is used instead of the chlorides of phosphorus, on account of the cheapness of the sulphur compound. Acetyl chloride is prepared by passing a mixture of chlorine and sulphur dioxide over anhydrous sodium acetate. In the presence of the salt sulphuryl chloride is first formed. 

Benzyl alcohol resembles ethyl alcohol in chemical properties. It yields an aldehyde and an acid on oxidation, is converted into benzyl chloride by the chlorides of phosphorus, and forms esters with acids. The presence of the phenyl radical affects... 

With chloride of phosphorus it forms chloride of antimony and sulphide of phosphorus, and also sulphophosphoride of antimony (Brandimont). 

Pore phosphorus is a colourless, or very pale, yellowish, transparent, or translucent solid, of the consistence of wax. Its sp. g. is 1-77. At 113° it melts, and at 572° it boils, distilling completely in close vessels. It has, in the solid form, neither taste nor smell but it gives off vapours in the air, which, undeigoing a slow combustion, have an odour of garlic and in solution it has an acrid disagreeable taste. Phosphorus is insoluble in water, soluble in alcohol, ether, oils, sulphuret of carbon, and chloride of phosphorus. From the latter liquids it is often deposited in octahedral and dodecahedral crystals. It is very poisonous, but is used in medicine in very small doses. 

Violent reactions can occur with halogens, halogenated hydrocarbons, nitroorganics, oxidizers, sulfur dioxide, and chlorides of phosphorus, arsenic, and antimony. With the latter compounds, diethylzinc forms pyrophoric triethylphosphine, triethyl arsine, and triethylstibine, respectively. 

The discovery of the liquid chloride of phosphorus had been announced by Gay-Lussac and Thenard in the Moniteur of 27 May 1808, which is quoted by Davy. The two French chemists were engaged in an extensive investigation of... 

In 1812 Davy described the formation of crystalline phosphorous acid by the action of water on liquid chloride of phosphorus (PCI3) and the production of phosphine, not spontaneously inflammable, on heating it. He attempted to determine the composition of the gas and of phosphorous (hydrophosphorous)... 

In 1818 he mentions Dulong s (see p. 199) and Berzelius s results and confirmed Dulong s discovery of hypophosphorous acid, but thought his phosphatic (hypophosphoric) acid a mixture. Davy by taking the proportional numbers or equivalents of oxygen as 15 and phosphorus 45 obtained what correspond with the formulae hypophosphorous acid P + 0, phosphorous acid P + 2O, and phosphoric acid P + 4O, all incorrect. He was unable to find the composition of liquid chloride of phosphorus (PCI3) by synthesis but from 13 6 gr. decomposed by water he obtained 43 gr. of silver chloride (correct 42 6) 3 gr. of phosphorus required about 20 (should be 17I) gr. of chlorine to form the sublimate (PCI5). Most of the experiments were made by Faraday. 

The two common chlorides of phosphorus, PCI3 and PCI5, both important in the production of other phosphorus compounds, coexist in equilibrium through the reaction... 

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