Phosphorous pentoxide

Trifluoromethanesulfonic acid anhydride, bp 84°C, is prepared by refluxing the acid over an excess of phosphorous pentoxide (18,26). The anhydride reacts instantaneously with ammonia or amines to form trifluoromethanesulfonamides. The anhydride reacts with most polar organic solvents. 

Reactions. Heating an aqueous solution of malonic acid above 70°C results in its decomposition to acetic acid and carbon dioxide. Malonic acid is a useful tool for synthesizing a-unsaturated carboxyUc acids because of its abiUty to undergo decarboxylation and condensation with aldehydes or ketones at the methylene group. Cinnamic acids are formed from the reaction of malonic acid and benzaldehyde derivatives (1). If aUphatic aldehydes are used acryhc acids result (2). Similarly this facile decarboxylation combined with the condensation with an activated double bond yields a-substituted acetic acid derivatives. For example, 4-thiazohdine acetic acids (2) are readily prepared from 2,5-dihydro-l,3-thiazoles (3). A further feature of malonic acid is that it does not form an anhydride when heated with phosphorous pentoxide [1314-56-3] but rather carbon suboxide [504-64-3] [0=C=C=0], a toxic gas that reacts with water to reform malonic acid. 

Selenium trioxide, SeO, is white, crystalline, and hygroscopic. It can be prepared by the action of sulfur trioxide on potassium selenate or of phosphorous pentoxide on selenic acid. It forms selenic acid when dissolved in water. The pure trioxide is soluble in a number of organic solvents. A solution in Hquid sulfur dioxide is a selenonating agent. It is stable in very dry atmospheres at room temperature and on heating it decomposes first to selenium pentoxide [12293-89-9] and then to selenium dioxide. 

Strong dehydrating agents such as phosphorous pentoxide or sulfur trioxide convert chlorosulfuric acid to its anhydride, pyrosulfuryl chloride [7791-27-7] S20 Cl2. Analogous trisulfuryl compounds have been identified in mixtures with sulfur trioxide (3,19). When boiled in the presence of mercury salts or other catalysts, chlorosulfuric acid decomposes quantitatively to sulfuryl chloride and sulfuric acid. The reverse reaction has been claimed as a preparative method (20), but it appears to proceed only under special conditions. Noncatalytic decomposition at temperatures at and above the boiling point also generates sulfuryl chloride, chlorine, sulfur dioxide, and other compounds. 

B. Bis[2,2,2-trifiuoro-l-phenyl-l- trijlucrromethyl[ethoxy] Diphenyl Sulfurane. Carbon tetrachloride is distilled directly from phosphorous pentoxide into a dry, 2-1., three-necked flask fitted with stoppers until... 

The checkers purchased trifluoroacetic acid from Aldrich Chemical Company, Inc., and distilled it from phosphorous pentoxide. The submitters point out that some trifluoroacetic anhydride, whose effects have not been fully investigated, is obtained under these conditions. The submitters prefer to use trifluoroacetic acid which has been distilled through a glass packed column without the use of a drying agent. 

Phosphorus compounds (phosphoric acid, phosphorous pentoxide, phosphorous oxychloride, phosphorous pentachloride, phosphorous pentasulphide)... 

Several groups have employed the Paal-Knorr condensation for the preparation of disubstituted diarylfurans. Miyashita converted dione 67 into 3,4-disubstituted-2,5-diarylfuran 68 in good yield using standard Paal-Knorr conditions. Lai demonstrated that 2,5-disubstituted-3,4-diarylfurans like 70 are available from dione 69 upon exposure to phosphorous pentoxide. ... 

Zinc-Copper Couple A 500-ml Erlenmeyer flask equipped for magnetic stirring is charged with a mixture of zinc powder (49.2 g, 0.75 g-atom) and hydrochloric acid (40 ml of 3 % aqueous solution). The contents of the flask are rapidly stirred for 1 minute, and the liquid is decanted. Similarly, the zinc is washed with the following three times with 40 ml of 3% hydrochloric acid solution, five times with 100 ml of distilled water, five times with 75 ml of 2 % aqueous copper sulfate solution, five times with 100 ml of distilled water, four times with 100 ml of absolute ethanol, and five times with 100 ml of absolute ether. These last ethanol and ether washes are decanted onto a Buchner funnel to prevent loss. The residue is collected by suction filtration, washed again with anhydrous ether, and dried in air. Finally, the zinc-copper couple is stored (20-24 hours) in a vacuum desiccator over phosphorous pentoxide. 

Catalysis by PhosphorousPentoxide (7) A 500-ml round-bottom flask is charged with a mixture of 1-ethynylcyclohexanol (40 g, 0.32 mole), 250 ml of dry benzene, and 10 g of phosphorous pentoxide. (The addition of the phosphorous pentoxide may be attended by considerable heating if the benzene is not well dried no particular disadvantage is found in this case, providing provision for initial cooling is made.) A condenser is attached to the flask, and the contents are refluxed gently (steam bath) for 2 hours. The cooled solution is then decanted from the phosphorous pentoxide, washed once with bicarbonate solution, and dried (anhydrous sodium sulfate). Removal of the benzene (rotary evaporator) and fractionation of the residue affords the desired product, bp 85-88°/22 mm, 1.4892, about 25 g (61 %). 

The submitters used reagent-grade dichloromethane without purification. The checkers dried dichloromethane by distillation from phosphorous pentoxide. 

The submitters added 5.88 ml. of aqueous 85% phosphoric acid to 3.98 g. of phosphorous pentoxide and heated the mixture for 15 minutes or until all of the solid had dissolved. The checkers placed 71.0 g. of phosphorous pentoxide in a flask, cooled it in ice, and cautiously added 27 ml. of water. 

First prepd by Hofmann and Zedtwitz (Ref 1) by passing a mixt of nitric oxide and nitrogen dioxide into 72% perchloric acid. The acid was then evapd at 140°, and on cooling the hydrate, N0C104.H2O, crystd out. The product was dehydrated in vacuo over phosphorous pentoxide When heated below 100° it decomps (Ref 2) according to the equation ... 

Apparent yields in excess of the theoretical amount may be observed owing to the presence of a small proportion of water. The oily product may be dried at high vacuum over phosphorous pentoxide for several days. 

A similar process allows reacting triethyl phosphate and phosphorous pentoxide to form a polyphosphate in an organic solvent [871]. An excess of 1.3 moles of triethyl phosphate with respect to phosphorous pentoxide is the most preferred ratio. In the second stage, a mixture of higher aliphatic alcohols from hexanol to decanol is added in an amount of 3 moles per 1 mole phosphorous pentoxide. Aluminum sulfate is used as a crosslinker. Hexanol results in a high-temperature viscosity of the gel, while maintaining at a pumpable viscosity at ambient temperatures [870]. 

A gel of diesel or crude oil can be produced using a phosphate diester or an aluminum compound with phosphate diester [740]. The metal phosphate diester may be prepared by reacting a triester with phosphorous pentoxide to produce a polyphosphate, which is then reacted with an alcohol (usually hexanol) to produce a phosphate diester [870]. The latter diester is then added to the organic liquid along with a nonaqueous source of aluminum, such as aluminum isopropoxide (aluminum-triisopropylate) in diesel oil, to produce the metal phosphate diester. The conditions in the previous reaction steps are controlled to provide a gel with good viscosity versus temperature and time characteristics. All the reagents are substantially free of water and will not affect the pH. 

In the first freeze drying plant [2.9] phosphorous pentoxide has been used to absorb the water vapor, but to day this technique is outdated. The development of refrigeration technology with compressors or NH3 absorption and the availability of LN2 has replaced water absorption by silica gel or similar products. Some trials aiming to revive this technology are detailed in Section 1.2.6. 

A. Trifluoromethanesulfonic Anhydride. To a dry, 100-ml., round-bottomed flask are added 36.3 g. (0.242 mole) of trifluoromethane-sulfonic acid (Note 1) and 27.3 g. (0.192 mole) of phosphorus pentoxide (Note 2). The flask is stoppered and allowed to stand at room temperature for at least 3 hours. During this period the reaction changes from a slurry to a solid mass. The flask is fitted with a short-path distilling head and then heated first with a stream of hot air from a heat gun and then with the flame from a small burner. The flask is heated until no more trifluoromethanesulfonic anhydride distills, b.p. 82-115°. The yield of the anhydride, a colorless liquid, is 28.4-31.2 g. (83-91%). Although this product is sufficiently pure for use in the next step of this preparation, the remaining acid may be removed from the anhydride by the following procedure. A slurry of 3.2 g. of phosphorous pentoxide in 31.2 g. of the crude anhydride is stirred at room temperature in a stoppered flask for 18 hours. After the reaction" flask has been fitted with a short-path distilling head, it is heated with an oil bath to distill iD.7 g. of forerun, b.p. 74—81°, followed by 27.9 g. of the pure trifluoromethanesulfonic acid anhydride, b.p. 81-84° (Note 3). 

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