Phosphorus oxychloride trichloride

Salicyl-u-toluide has been prepared only by the action of phosphorus oxychloride upon a mixture of salicylic acid and o-toluidine. The useful methods of preparation of salicylanilide are by the interaction of salicylic acid and aniline in the presence of phosphorus trichloride, by heating phenyl salicylate and aniline, and from o-hydroxybenzamide and bromobenzene in the presence of small amounts of sodium acetate and metallic copper. A number of these and other anilides have been described. ... 

Bischloromethyl ether has been prepared by saturation of formalin with dry hydrogen chloride by the reaction of paraformaldehyde with phosphorus trichloride or phosphorus oxychloride, by solution of paraformaldehyde in concentrated sulfuric acid and treatment with ammonium chloride or dry hydrogen chloride, and by suspension of paraformaldehyde in seventy or eighty percent sulfuric acid and treatment with chlorosulfonic acid. It is formed together with the asymmetrical isomer when methyl ether is chlorinated and when paraformaldehyde is treated with chlorosulfonic acid. The present method has been published. ... 

These formulae explain the scission products of the two alkaloids and the conversion of evodiamine into rutaecarpine, and were accepted by Asahina. A partial synthesis of rutaecarpine was effected by Asahina, Irie and Ohta, who prepared the o-nitrobenzoyl derivative of 3-)3-amino-ethylindole-2-carboxylic acid, and reduced this to the corresponding amine (partial formula I), which on warming with phosphorus oxychloride in carbon tetrachloride solution furnished rutaecarpine. This synthesis was completed in 1928 by the same authors by the preparation of 3-)S-amino-ethylindole-2-carboxylic acid by the action of alcoholic potassium hydroxide on 2-keto-2 3 4 5-tetrahydro-3-carboline. An equally simple synthesis was effected almost simultaneously by Asahina, Manske and Robinson, who condensed methyl anthranilate with 2-keto-2 3 4 5-tetrahydro-3-carboline (for notation, see p. 492) by the use of phosphorus trichloride (see partial formulae II). Ohta has also synthesised rutaecarpine by heating a mixture of 2-keto-2 3 4 5-tetrahydrocarboline with isatoic anhydride at 195° for 20 minutes. 

The difficulties encountered in the synthesis of 2-alkyl- and 2-aryl-substituted selenazoles lie principally in the preparation of the corresponding selenoamides. In this respect, a method is worthy of note in which the use of selenoamides is dispensed with. For this, a nitrile, a hydrogen selenide, and an a-halogenoketone are reacted together in the presence of a condensation catalyst. Phosphorus oxychloride, alone or mixed with zinc chloride or phosphorus trichloride, is specially suitable. The yields of the corresponding 2-alkylseIenazoles are up to a maximum of 25%,... 

Dangerous materials may require special equipment. Chlorination with gaseous chlorine requires quite expensive storage facilities. Chlorination with chlorine, thionyl chloride, sulphuryl chloride, phosphorus oxychloride, phosphorus trichloride, or phosphorus pentachloride, all of which are fairly hazardous, requires off-gas treatment. Some of these reactants can be recycled. Pyrophoric solids such as hydrogenation catalysts, anhydrous aluminium trichloride for Friedel-Crafts reactions, or hydrides used as reducing agents should usually be handled using special facilities. Therefore, all of the above proce.sses are usually carried out in dedicated plants. 

The reactants initially form a paste that may form sizable lumps upon agitation, but the mixture liquifies upon further reaction as the result of the production of phosphorus oxychloride (POCI3) and phosphorus trichloride (PCI3). 

The product may be obtained from tetraethyldiaminobenzophenone and N-ethylnaphthylamine with phosphorus oxychloride or with phosphorus trichloride, the route parallels the synthesis of Crystal Violet. The resulting colorant is the basic dye for Pigment Blue 1. 

In many cases the solid, more active and much less volatile pentar chloride is used instead of phosphorus trichloride. Then it is necessary to use a whole mole of PC15 for each mole of alcohol since the reaction leads to the formation of the much more -sluggish phosphorus oxychloride, e.g. 

Phenylbenzbyldiazomethane, 48 Phenyl cinnamate, 77 o-Phenylenediamine, 10 Phosphorus oxychloride, 11 Phosphorus trichloride, 106 Photoflood lamps, 84, 104 Phthalic anhydride, 70 Phthalic monoperacid, 70 Phthaloyl chloride, 51 a-Picoline, 79... 

The phosphate manufacturing and phosphate fertilizer industry includes the production of elemental phosphorus, various phosphorus-derived chemicals, phosphate fertilizer chemicals, and other nonfertilizer phosphate chemicals [1-30], Chemicals that are derived from phosphorus include phosphoric acid (dry process), phosphorus pentoxide, phosphorus penta-sulfide, phosphoms trichloride, phosphorus oxychloride, sodium tripolyphosphate, and calcium phosphates [8]. The nonfertilizer phosphate production part of the industry includes defluori-nated phosphate rock, defluorinated phosphoric acid, and sodium phosphate salts. The phosphate fertilizer segment of the industry produces the primary phosphorus nutrient source for the agricultural industry and for other applications of chemical fertilization. Many of these fertilizer products are toxic to aquatic life at certain levels of concentration, and many are also hazardous to human life and health when contact is made in a concentrated form. 

Weeks MH, Musselman NP, Yevich PP, et al Acute vapor toxicity of phosphorus oxychloride, phosphorus trichloride and methyl phos-phonic dichloride. Am Ind Hyg Assoc J 25 470-475, 1964... 

Phosphorus oxychloride can be prepared from phosphorus trichloride or phosphorus pentachloride. It can be obtained from phosphorus trichloride by cautious addition of potassium chlorate ... 

When the vapors of phosphorus oxychloride are passed over carbon at red heat, phosphorus trichloride is produced ... 

Phosphorus trichloride also can be prepared by reducing phosphorus oxychloride vapors with carbon at red heat ... 

Substituted phenyl salicylates can be prepared by heating salicylic acid and the appropriate phenol in the presence of phosphorus oxychloride,34 5 phosphorus trichloride,4 5 phosphorus pentachloride,4 6 phosgene,4 or thionyl chloride,4 or by heating the phenol and salol.7... 

Phosphorus Bromide Phosphorus Oxychloride Phosphorus Pentasulfide Phosphorus Persulfide Phosphorus Tribiomide Phosphorus Trichloride... 

Phosphorous dichlonde, phenyl-, 55, 128 Phosphorous oxy trichloride, 57, 103 Phosphorous pentachlonde, 57, 63,58, 68 Phosphorus oxychloride, 56, 4 Phosphorus triamide, hexaethyl-, 58, 143 Photocycloaddition reactions, 57, 116 Photolysis, apparatus for, 55,17 Phth-Gly Gly-OEt, 56, 93... 

Phenyl iso-thiocyanate, 642,643 Phenylthioureas, 422, 655 Phenylurea, 644, 645 Phenylurethanos, 264 Phloroacetophenone, 727, 736 Phosgene, 185 Phosphoric acid, 189, 284 Phosphorus, detection of, 1043 Phosphorus, red, purification of, 193 Phosphorus oxychloride, 367 Phosphorus pentabromide, 489, 492 Phosphorus pentachloride, 799, 822, 974 Phosphorus pentoxide, handling of, 407 Phosphorus tribromide, 189, 492 Phosphorus trichloride, 367 Phosphorus trisulphide," 836 Phthalamide, 983 Phthalein test, 681 ... 

Like sulphuryl chloride, pyrosulphuryl chloride can convert many elements, e.g. sulphur, phosphorus, antimony and mercury, into the corresponding chlorides, with simultaneous formation of sulphur dioxide and trioxide.2 In the reaction between pyrosulphuryl chloride and phosphorus pentachloride or trichloride, there are obtained phosphorus oxychloride, sulphur dioxide and chlorine. 

Phosphorus pentaehloride acts on selenium dioxide with the formation of the tetrachloride, whilst phosphorus trichloride yields brown amorphous selenium in these reactions phosphorus oxychloride is also formed. 

Eighty grams of bromine are slowly added to 69g of phosphorus trichloride contained in a flask well protected from moisture. The reaction vessel is cooled in an ice-water bath while dry sulfur dioxide is passed into the mixture until the gain in weight is 32g, corresponding to the theoretical uptake of the gas. Gareful fractionation as in methods (I) or (II) yields 85-90% of pure product. The by-product of phosphorus oxychloride, which distills over first, may be collected by cooling the distillation receiver to about —10°C or lower. 

The oxygen of ketone and aldehyde groups is readily replaced by halogen under the influence of phosphorus trichloride or pentachloride the reaction may be carried out with or without a solvent solvents commonly employed are chloroform, benzene, petroleum ether, acetyl chloride and phosphorus oxychloride. 

U. J. J. Leverrier exposed to air a soln. of phosphorus in ether or in phosphorus trichloride, washed the product in warm water, and dried it in vacuo over sulphuric acid. The analysis corresponded with phosphorus tetritoxide, P40. B. Reinitzer and H. Goldschmidt obtained a similar product by the action of phosphorus oxychloride on zinc, magnesium, or aluminium at 100°, or on yellow phosphorus at 250°. They added that the substance obtained with yellow phosphorus has the composition of phosphorus tetritoxide, but not its properties. Its properties approximate closely to those of red phosphorus. 

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