Phosphorus excess

In conclusion, it should be noted that we live in an environment with a permanent phosphorus excess. This factor, resulting from the wide use of phosphate-containing detergents, fertilizers and food additives may have some negative effects on the environment and human health. The biochemistry of PolyPs may offer new ways for overcoming unfavourable factors caused by phosphate contamination of the environment and for controlling infections and some other diseases. 

Although phosphorus is not directly toxic in the forms and amounts found naturally in the environment, plants supplied with a small phosphorus excess often develop purple to rusty-brown lesions on their dark-green leaves. Growth is not impaired, when excess of phosphorus is applied in small amounts, but plants supplied with a large excess lack vigor and have short stout the leaves are dark green in color... 

PCI3 r.d. 1.57 m.p. -112°C b.p. 75.5°C. it is soluble in ether and in carbon tetrachloride but reacts with water and with ethanol, it may be prepared by passing chlorine over excess phosphorus (excess chlorine contaminates e product with phosphorus(V) chloride). The molecule is pyramidal in the gas phase and possesses weak electron-pair donor properties, it is hydrolysed violently by water to phosphonic acid and hydrogen chloride. Phosphorus(lll) chloride is an important starting point for the synthesis of a variety of inorganic and organic derivatives of phosphorus. 

Excess of calcium over phosphorus excess of phosphorus over calcium----If the diet contains an excess of cal-... 

Phosphorus(lII) oxide, P4O6, phosphorus trioxide, m.p. 24°C, b.p. 174 C. A waxy material (burn P in deficiency of O2)- It burns in excess O2 to P2OJ, reacts with, e.g. CI2 to POCI3 and dissolves in water to give phosphorus(TII) oxyacids. The structure is similar to that of P40,o but without the terminal oxygens. 

Phosphorus trichloride reacts with chlorine in excess to give phosphorus pentachloride, an equilibrium being set up ... 

Phosphorus pentachloride is prepared by the action of chlorine on phosphorus trichloride. To push the equilibrium over to the right, the temperature must be kept low and excess chlorine must be present. Hence the liquid phosphorus trichloride is run dropwise into a flask cooled in ice through which a steady stream of dry chlorine is passed the solid pentachloride deposits at the bottom of the flask. 

Chlorine reacts with most elements, both metals and non-metals except carbon, oxygen and nitrogen, forming chlorides. Sometimes the reaction is catalysed by a trace of water (such as in the case of copper and zinc). If the element attacked exhibits several oxidation states, chlorine, like fluorine, forms compounds of high oxidation state, for example iron forms iron(III) chloride and tin forms tin(IV) chloride. Phosphorus, however, forms first the trichloride, PCI3, and (if excess chlorine is present) the pentachloride PCI5. 

Hydrogen iodide. This gas may be conveniently prepared by allowing a solution of two parts of iodine in one part of hydriodic acid, sp. gr. 1 7 (for preparation, see Section 11,49,2), to drop on to excess of red phosphorus. The evolution of hydrogen iodide takes place in the cold when the evolution of gas slackens considerably, the mixture should be gently warmed. 

Dibromobutane (from 1 4-butanediol). Use 45 g. of redistilled 1 4-butanediol, 6-84 g. of purified red phosphorus and 80 g. (26 ml.) of bromine. Heat the glycol - phosphorus mixture to 100-150° and add the bromine slowly use the apparatus of Fig. Ill, 37, 1. Continue heating at 100-150° for 1 hour after all the bromine has been introduced. Allow to cool, dilute with water, add 100 ml. of ether, and remove the excess of red phosphorus by filtration. Separate the ethereal solution of the dibromide, wash it successively with 10 per cent, sodium thiosulphate solution and water, then dry over anhydrous potassium carbonate. Remove the ether on a water bath and distil the residue under diminished pressure. Collect the 1 4-dibromobutane at 83-84°/12 mm. the yield 3 73 g. 

An equivalent result may be obtained by treating excess of sodium acetate with phosphorus oxychloride acetyl chloride is an intermediate product and the final result is ... 

Place 125 ml. of glacial acetic acid, 7 -5 g. of purifled red phosphorus (Section II,50,d) and 2 5 g. of iodine in a 500 ml, round-bottomed flask fitted with a reflux condenser. Allow the mixture to stand for 15-20 minutes with occasional shaking until aU the iodine has reacted, then add 2 5 ml. of water and 50 g, of benzilic acid (Section IV,127). Boil the mixture under reflux for 3 hours, and filter the hot mixture at the pump through a sintered glass funnel to remove the excess of red phosphorus. Pour the hot filtrate into a cold, weU-stirred solution of 12 g. of sodium bisulphite in 500 ml, of water the latter should be acid to litmus, pro duced, if necessary, by passing sulphur dioxide through the solution. This procedure removes the excess of iodine and precipitates the diphenyl-acetic acid as a fine white or pale yellow powder. Filter the solid with suction and dry in the air upon filter paper. The yield is 45 g., m.p. 

Decane-1 10-dicarboxylic acid from sebacic acid. Convert sebacic acid into the acid chloride by treatment with phosphorus penta-chloride (2 mols) and purify by distillation b.p. 146-143°/2 mm. the yield is almost quantitative. Dissolve the resulting sebacoyl chloride in anhydrous ether and add the solution slowly to an ethereal solution of excess of diazomethane (prepared from 50 g. of nitrosomethylurea) allow the mixture to stand overnight. Remove the ether and excess of diazomethane under reduced pressure the residual crystalline 1 8-bis-diazoacetyloctane weighs 19 -3 g. and melts at 91° after crystaUisation from benzene. 

The synthesis of vitamin Dj from a sensitive dienone was another etu-ly success of phosphorus ylide synthesis (H.H. Inhoffen, 1958 A). This Wittig reaction could be carried out without any isomerization of the diene. An excess of the ylide was needed presumably because the alkoxides formed from the hydroxy group in the educt removed some of the ylide. 

Phosphorus Disorders. Phosphoms nutrient deficiency can lead to rickets, osteomalacia, and osteoporosis, whereas an excess can produce hypocalcemia. Faulty utilisation of phosphoms results in rickets, osteomalacia, osteoporosis, and Paget s disease, and renal or vitamin D-resistant rickets. 

Phosphorus pentacfaloride [10026-13-8] M 208.2, m 179-180 (sublimes). Sublimed at 160-170° in an atmosphere of chlorine. The excess chlorine was then displaced by dry N2 gas. All subsequent manipulations were performed in a dry-box [Downs and Johnson J Am Chem Soc 77 2098 1955]. Fumes in moist air. HARMFUL VAPOURS. 

Triazole has been prepared by the oxidation of substituted 1,2,4-triazoles, by the treatment of urazole with phosphorus pentasulfide, by heating equimolar quantities of formyl-hydrazine and formamide, by removal of the amino function of 4-amino-l,2,4-triazole, by oxidation of l,2,4-triazole-3(5)-thiol with hydrogen peroxide, by decarboxylation of 1,2,4-triazole-3(5)-carboxylic acid, by heating hydrazine salts with form-amide,by rapidly distilling hydrazine hydrate mixed with two molar equivalents of formamide, i by heating N,N -diformyl-hydrazine with excess ammonia in an autoclave at 200° for 24 hours, and by the reaction of 1,3,5-triazine and hydrazine monohydrochloride. ... 

Isopropyl Iodide.—The replacement of hydroxyl by iodine in the action of phosphorus and iodine on alcohols has alieady been described (see Piep. 6, p. 68), but here the presence of an excess of hydriodic acid, which is due to the action of water on the phosphorus iodide,... 

Trichloro-s-triazine also reacts readily with carbon or phosphorus nucleophiles. Diethylmalonate anion forms a mono-derivative under mild conditions and the tri-substitution product (327) under vigorous conditions with excess nucleophile. Nucleophilic attack by the 7r-electrons of ketene diethylacetal to give 254 and of dimethylaniline to give 253 has been mentioned earlier. Two... 

If the reaction temperature is raised to 430 K and the carbon monoxide pressure to 3 atm, coordination of the metal atom in the rearranged product occurs via the phosphorus site, as in 159 (M = Cr, Mo, W) [84JOM(263)55]. Along with this product (M = W) at 420 K, formation of the dimer of 5-phenyl-3,4-dimethyl-2//-phosphole, 160 (the a complex), is possible as a consequence of [4 - - 2] cycloaddition reactions. Chromium hexacarbonyl in turn forms phospholido-bridged TiyP)-coordinatedcomplex 161. At 420 K in excess 2,3-dimethylbutadiene, a transformation 162 163 takes place (82JA4484). 

The formation of the dichlorides is aided by increased temperature (60-80°C) and by an excess of PCI5 (2-2.3 moles/mole of 4-acetylpyrazole). With a larger excess of PCI5, further chlorination of the compounds occurs. With 3 moles of phosphorus pentachloride at 80°C in benzene, ketones 12a-d gave pyrazolyl-trichloroethylenes 16a-d in 75% yield. Then dichlorides 17a-d were converted quantitatively into pyrazolyltrichloroethylenes 16a-d in 1 h under the same conditions. 

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