Phosphorus tribromide

Reacts violently with water, forming hydrobromic acid and phosphorous acid.2 

Calcium Hydroxide and Sodium Carbonate. Disposal by slow addition to sodium carbonate and dry slaked lime resulted in a violent reaction.3 Potassium. PBr3 liquid or vapor ignites on contact with K.4 

Sodium. Na floats on liquid PBr3, but addition of a little water causes a violent explosion5 mixture of Na with PBr3 is shock sensitive.6 

Reacts rapidly with warm water, and reacts violently with limited quantities.7 

Vapor severely irritates the respiratory system. The vapor irritates and the liquid burns the eyes and skin. Swallowing assumed to cause severe internal irritation and damage. Prolonged exposure to low concentrations of vapor may cause damage to lungs. Avoid breathing vapor. Prevent contact with eyes and skin.2 

Test solutions of monosodium phosphate, NaH2PC 4, disodium phosphate, Na2HP04, and trisodium phosphate, Na3PC 4, with litmus paper. See pages 116-117. Explain how a compound can be an acid salt and react alkaline to litmus. 

List the solubilities of the three sodium phosphates. How would you prepare each from phosphoric acid  

Phosphorus reacts directly with bromine to form two compounds. With an excess of phosphorus the tribromide, PBr3, is formed the pentabromide, PBr5, results from the use of an excess 

Apparatus special Pyrex test tube 1 inch in diameter and 24 inches long. 

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The hydrolysis of phosphorus tribromide or triiodide is used in the preparation of hydrogen bromide and hydrogen iodide respectively ... 

The conversion of an aliphatic carboxylic acid into the a-bromo- (or a-chloro ) acid by treatment with bromine (or chlorine) in the presence of a catal3rtic amount of phosphorus tribromide (or trichloride) or of red phosphorus is known as the Hell-Volhard-Zelinsky reaction. The procedure probably involves the intermediate formation of the acyl halide, since it is known that halogens react more rapidly with acyl haUdes than with the acids themselves ... 

To 200 ml of 48% hydrobromic acid was added 0.40 mol of phosphorus tribromide (note 1). The mixture was agitated vigorously, while the temperature was kept between 20 and 30 0 by cooling in a water-bath at 10-15 0. After about 1 h the lower layer had disappeared completely. The solution was cooled to 0°C, then 0.40 mol of ammonium bromide, 0.10 mol (note 2) of copper(I) bromide (commercial product),... 

Note 1. The concentration of the aqueous HBr solution is increased by conversion of phosphorus tribromide with water. If available, a corresponding amount of gaseous HBr can be introduced into the 48% solution at 0°C. 

The most suitable synthetic method for these products is the heterocyc-lization reaction of N-thioacyl derivatives of amino acids (202) with phosphorus tribromide (378, 442-450, 559, 560) or anhydrous trifluoroacetic acid (448, 449, 451, 452) (Scheme 103). Treatment of N-thioacyl amino acids with acetic anhydride leads directly to the thiazolylacetate without isolation of an intermediate thiazolinone (365. 452). 2-Alkoxy-derivatives of A-2-thiazoline-5-one, however, can be obtained without acetylation by this method (453, 454). 

Carbon disulfide readily reacts with a-aminonitriles giving 2-mercapto-5-aminothiazoles (213), (271, 293) which can be converted to 5-aminothiazoles unsubstituted in the 2-position (Scheme 110 and Table II-34a). If this reaction is carried out in the presence of benzyl chloride in phosphorus tribromide, a 2-S-substituted thiazole derivative (214) is obtained in quantitative yield (Scheme 111), with R = hydrogen or phenyl (68, 304). 

Substituted 5-hydroxythiazoles (267b), Rj = alkylmercapto, acyl-amino, and sec-amino, are prepared by cydization of N-thioacyl-amino acids (266) with phosphorus tribromide or acetic anhydride (Scheme 137) (317, 350). i en the cydization of 266, R2 = H, is carried out with acetic anhydride in the presence of benzaldehyde (317, 325) or ethylformate (317), the benzylidene (268), R2=Ph, Rj = SR or CH2Ph, or 4-ethoxymethylene (268), Rj = SR and R2 = OEt, derivative is obtained directly (Scheme 138). 

Thionyl chloride and phosphorus tribromide are specialized reagents used to bring about particular functional group transformations For this reason we won t present the mechanisms by which they convert alcohols to alkyl halides but instead will limit our selves to those mechanisms that have broad applicability and enhance our knowledge of fundamental principles In those instances you will find that a mechanistic understand mg IS of great help m organizing the reaction types of organic chemistry... 

Reaction of alcohols with phosphorus tribromide (Section 4 13) As an alternative to converting alco hols to alkyl bromides with hydrogen bromide the inorganic reagent phosphorus tribromide is some times used... 

Reaction with phosphorus trihalides (Section 4 13) Phosphorus trichloride and phosphorus tribromide convert alcohols to alkyl halides... 

This method of a bromination of carboxylic acids is called the Hell-Volhard-Zelinsky reaction This reaction is sometimes carried out by using a small amount of phosphorus instead of phosphorus trichloride Phosphorus reacts with bromine to yield phosphorus tribromide as the active catalyst under these conditions... 

Phosphorus tribromide Potassium, ruthenium tetroxide, sodium, water... 

In view of the high price and other difficulties associated with the use of phosphoryl bromide, the transhalogenation of 2-chloro- and 2-chloro-4,6-dimethyl-pyrimidine (919) by treatment with inexpensive phosphorus tribromide to give their bromo analogues in >50% yield, assumes potential importance as a general method (67JCS(C)1204). 

Section 5.10.3.2). Treatment of methyl 6-phthalimido penicillinate (jR)-sulfoxide (40) with JV-chlorosuccinimide in refluxing carbon tetrachloride gives an epimeric mixture of sulfinyl chlorides (41) which are ring closed to epimeric 3-methylenecepham sulfoxides (42a) using tin(IV) chloride. Reduction with phosphorus tribromide gives the desired methyl 7-phthalimido-3-methylenecepham 4-carboxylate (42b). 

Ethylene bromohydrin has been prepared by the reaction between ethylene glycol and hydrobromic acid and phosphorus tribromide. It has also been prepared by the direct addition of hypobromous acid to ethylene, and by the reaction between ethylene and dilute bromine water. With ethylene oxide now available at a reasonable price, the method described is probably the best because of the high yields and the convenience of reaction. 

Glycerol a,7-dibromohydrin has been prepared from glycerol and phosphorus tribromide from glycerol and bromine from glycerol, red phosphorus, and bromine. ... 

The temperature must be raised slowly to avoid formation of spontaneously inflammable hydrides of phosphorus whict will ignite and destroy the preparation. A similar result occur if the phosphorus tribromide is added at 170°. 

Pentaerythrityl bromide has been prepared by the action of phosphorus tribromide on pentaerythritol, - and of an acetic acid solution of hydrobromic acid on pentaerythritol tetraacetate. The iodide has been prepared by the action of red phosphorus and hydriodic acid on pentaerythritol and by treating the bromide with sodium iodide in acetone. ... 

Tetramethylene chlorohydrin may be converted to the chlorobromide in excellent yields by the action of phosphorus tribromide. ... 

Alkyl halides are such useful starting materials for preparing other functional group types that chemists have developed several different methods for converting alcohols to alkyl halides. Two methods, based on the inorganic reagents thionyl chloride and phosphorus tribromide, bear special mention. 

Phosphorus tribromide reacts with alcohols to give alkyl bromides and phosphorous acid. 

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