Phosphorus Chloride oxidations

About 80-90% of the elemental P produced is reoxidized to (pure) phosphoric acid (p. 521). The rest is used to make phosphorus oxides (p. 503). sulfides (p. 506), phosphorus chlorides and oxochloride (p. 4%). and organic P compounds. A small amount is convened to red phos rftorus (see below) for use in the striking surface of matches for pyrotechnics and as a flame retarding agent (in polyamides). Bulk price for P4 is S2.00/kg. 

Chlor-oxyd, n. chlorine oxide, -phosphor, m. phosphorus chloride, -pikrin, n. chloropicrin. -platin, n. platinic chloride, -platinsiiure,. chloroplatinic acid, -quecksilber, n. mercury chloride (either one), -raucherung, /. chlorine fumigation. 

EXAMPLE 13.13. Name the following according to the Stock system (a) FeCl, (6) U02S04, and (c) P4O10. (a) Iron(II) chloride, (b) dioxouranium(VI) sulfate, and (c) phosphorus(V) oxide. 

The KB9C2H10(CH3)2 recovered from the ethanol solution is dissolved in 150 ml. of water, and a solution of 22 g. of trimethylammonium chloride in 100 ml. of water is added slowly with vigorous stirring. The precipitated salt is isolated by filtration, washed once with 50 ml. of cold water, and dried in vacuum over phosphorus(Y) oxide. The yield of (CH3)3NHB9C2Hio-(CH3)2 is 37.8 g. (98%). To purify the salt by crystallization, a boiling solution of 38 g. of the salt in 2 1. of water is allowed to cool slowly to 0°. Eighty per cent of the material is recovered in the first crop. Successive crops of the trimethylammonium salt may be obtained, or the anion may be recovered as the less soluble tetramethylammonium salt by addition of an aqueous solution of tetramethylammonium chloride to the mother liquor. The tetramethylammonium salt may be recrystallized from an ethanol-water solution. 

Drying with Phosphorus V) Oxide. If no zeolite is available, phosphorus(V) oxide may be used. Put 500 ml of diethyl ether and 50 g of phosphorus(V) oxide into a one-litre flask provided with a stopper and a calcium chloride tube filled with calcium chloride. Mix the contents of the flask from time to time by carefully shaking it and let the mixture stand for two days. Then pour off the ether from the black oily liquid at the bottom of the flask and distil the ether over metallic sodium. 

Preparation of Macrocrystalline Iron(III) Oxide. Assemble an apparatus for preparing hydrogen chloride. To dry the gas well, install a column with phosphorus(V) oxide in addition to two wash bottles with sulphuric acid. Spill amorphous iron(III) oxide into the middle part of a three-section quartz tube (Fig. 136). Put the latter into a two-zone furnace. To retain the temperature difference, wrap the unheated zone (the middle of the tube) with asbestos. 

Succinic anhydride has been obtained by distillation of succinic acid with phosphorus pentachloride, or from benzoyl chloride and sodium succinate.1 It has been prepared from succinic acid and phosphorus oxychloride or phosphorus pentachloride 2 by distillation of succinic acid with phosphorus pent-oxide 3 from acetyl chloride and barium succinate, or from sue-cinyl chloride and sodium acetate 4 from ethyl succinate and benzoyl chloride 5 from succinic acid and acetyl chloride, or from sucdnyl chloride and oxalic acid 6 from succinic acid and suc-cinyl chloride from succinic acid and acetic anhydride 7 from succinic add and acetyl chloride 8 and from sodium succinate and acetic anhydride.9... 

Twenty grams of phosphorus (V) oxide are quickly introduced into an all-glass distilling apparatus fitted with an air condenser, and 30g of chlorosulfonic acid (No. 87) are then added. The mixture is heated slowly and the distillate is collected in a receiver protected from atmospheric moisture. The crude product is refractionated to yield 20 25g of the chloride, which boils at 146-153°C with slight decomposition. 

Diethyl phosphite was probably first prepared in 1854 by the reaction between alcohol and phosphorus(III) chloride.1 It can also be prepared from phosphorus(III) oxide and alcohol,2 from phosphorous acid and diazoethane,3 or from lead phosphite and ethyl iodide.4... 

Five and twenty-three hundredths grams of germanium(IV) oxide (0.05 mol) is dissolved in 15 ml. of a concentrated aqueous solution of hydrofluoric acid (47 %). A platinum evaporating dish or a polyethylene plastic beaker is used to keep silicon contamination to a minimum. A solution of 10.5 g. of barium chloride (0.05 mol) in 50 ml. of water is added. Barium hexafluorogermanate forms as a white, granular precipitate, which is filtered and washed free of chloride. The product is dried by heating to 300° in vacuo and is stored in a desiccator over phosphorus(V) oxide. The yield is 15.24 g. (94%). 

With the exception of those halogenopyrazines made by primary synthesis (see Chapters 1 and 2), most chloropyrazines have been made recently by the reaction of tautomeric pyrazinones with a phosphorus chloride or by the reaction of pyrazine iV-oxides with phosphoryl chloride in contrast, most other halogenopyrazines have been made by direct halogenation or by transhalogenation of chloropyrazines. A single interesting example of the conversion of a methoxy- into a chloropyrazine is included at the end of Section 4.1.1. 

The mixture remaining in the three-necked flask is stored overnight at 0°. The solid product is then freed of oily contaminants by spreading on clay plates, which are stored in a desiccator. Finally, the solid is washed with 100 ml. of ice water and then dried in a desiccator over phosphorus(V) oxide. The crude product so obtained is recrystallized twice from 10-15 times its weight of n-heptane which has been previously dried over sodium wire. M.P., 144-145°. Yield, based upon (tri-chlorophosphoranylidene)sulfamoyl chloride, is ca. 12 g. (17%). Anal. Calcd. for N3S3O3CI3 N, 14.36 S, 32.87 Cl, 36.36 mol. wt., 292.57. Found N, 14.51 S, 32.44 Cl, 36.84 mol. wt., 300. 

Am. (a) Nickel(II) chloride (b) dioxouranium(VI) sulfate (c) phosphorus(V) oxide... 

Ignition on contact with furfuryl alcohol powdered metals (e.g., magnesium iron) wood. Violent reaction with aluminum isopropoxide -f- heavy metal salts charcoal coal dimethylphenylphosphine hydrogen selenide lithium tetrahydroaluminate metals (e.g., potassium, sodium, lithium) metal oxides (e.g., cobalt oxide, iron oxide, lead oxide, lead hydroxide, manganese oxide, mercur oxide, nickel oxide) metal salts (e.g., calcium permanganate) methanol + phosphoric acid 4-methyl-2,4,6-triazatricyclo [5.2.2.0 ] undeca-8-ene-3,5-dione + potassium hydroxide a-phenylselenoketones phosphorus phosphorus (V) oxide tin(II) chloride unsaturated organic compounds. 

An oxidant. Combusdble when exposed to heat and flame. Moderate explosion hazard when exposed to heat or flame. Explosive reacdon with solid or concentrated alkali + heat (e.g., sodium hydroxide or potassium hydroxide), aluminum chloride + phenol (at 120°C), aniline + glycerol + sulfuric acid, nitric + sulfuric acid + heat. Forms explosive mixmres with aluminum chloride, oxidants (e.g., fluorodinitromethane, uranium perchlorate, tetranitromethane, sodium chlorate, nitric acid, nitric acid + water, peroxodisulfuric acid, dinitrogen tetraoxide), phosphorus pentachloride, potassium, sulfuric acid. Reacts violendy with aniline + glycerin, N2O, AgC104. To fight fire, use water, foam, CO2, dry chemical. Incompadble with potassium hydroxide. When heated to decomposidon it emits toxic flames of NOx. See also NITRO COMPOUNDS OF AROMATIC HYDROCARBONS. 

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