Oxychlorides

In this light, a simple path for the important reaction of 

Further chlorination of S2CI2 yields a red dichloride, SCU (boiling point 59° C), whereas the further chlorination of Se2Cl2 yields a white tetrachloride, SeCl4. The latter compound may lose two of its chlorines (presumably as radicals) upon vaporization, (SeCl4 SeCl2 + Cl2) and may lose one of its chlorines (as an ion) on treatment with the Lewis acids AuCl3 and SbCL  

SeCU + AuCL - SeClJAuCIr SeCl4 + SbCls SeCtfSbCl  

Selenium oxychloride should be handled with respect, its action on human skin being comparable to that of liquid bromine. 

Gillespie, R. J., and Robinson, E. A. The Sulfuric Acid Solvent System, in Emeleua and Sharpe s Advances in Inorganic Chemistry and Radiochemistry, Yol. I., 386-424, Academic Press Inc., New York (1959). 

Chromium oxychloride Cr02Cl2 [1758] Phosphorus oxychloride POCI3 [1810] Nitrosyl chloride NOCl [1069] Sulphuryl chloride SO2CI2 [1834] Thionyl chloride SOCI2 [1836] 

Oxychlorides have the general formula MOCl. They decompose in the presence of water and release hydrochloric acid that attacks aluminium. This applies to thionyl chloride SOCI2, sulfuryl chloride SO2CI2, nitrosyl chloride NOCl, phosphoryl chloride POCI3, chromium oxychloride Cr02Cl2, bismuth oxychloride BiOCl and copper oxychloride CuOCl. The latter is, like copper sulphate, widely used as an anticryptogamide for the treatment of certain diseases of fhiit trees and vine. 

Anonyme, Corrosion data survey. Section 1 Main tables, NACE Engineers, 1985, p. 124, 167. Bollinger J., Uber die Kotrosion verschiedener Metalle in verflusigtem Schwefedioxyd, Schweizer Archiv, vol. 10, 1952, p. 321. 

Shukotin A.M., Lantratova N.Y., Gerasimova V.A., Corrosion resistance of metallic materials in nitrogen oxides at high temperature and pressures, 1968, Translated from Russian, Document ORNL-TR-2539. 

Tatu H., Le blanchiment a I eau oxygenee. Revue de VAluminium, no. 55,1933, p. 2077-2089. Alley C.W., Hayford A.W., Scott H.F., Nitrogen tetroxyde corrosion studies, P. B. Report 171 301 U.S. Department of Commerce. 1960. 

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CH3)2N]3P0. M.p. 4°C, b.p. 232"C, dielectric constant 30 at 25 C. Can be prepared from dimethylamine and phosphorus oxychloride. Used as an aprotic solvent, similar to liquid ammonia in solvent power but easier to handle. Solvent for organolithium compounds, Grignard reagents and the metals lithium, sodium and potassium (the latter metals give blue solutions). 

The reaction with oxygen converts phosphorus trichloride to phosphorus trichloride oxide (oxychloride), POCI3 the trichloride is able to remove oxygen from some molecules, for example sulphur trioxide... 

The oxide dichloride, b.p. 351 K, is separated from the less volatile phosphorus oxychloride by a fractional distillation. 

One disadvantage of this method is that it is sometimes difficult to separate the acid chloride sharply from the phosphorus oxychloride by fractional dis tillation, and unless the boiling oints of these two substances are fairly wide apart, traces of the oxychloride will occasionally pass over in the vapour of the acid chloride. If, however, thionyl chloride is used instead of phosphorus... 

This preparation illustrates the use of phosphorus pentachloride for the preparation of acyl chlorides in this case no difficulty is experienced in separating the 3,5-dinitrobenzoyl chloride from the phosphorus oxychloride formed simultaneously (c/. p. 240), because the former is readily isolated as a crystalline... 

Assemble in a fume-cupboard the apparatus shown in Fig. 67(A). Place 15 g. of 3,5-dinitrobenzoic acid and 17 g. of phosphorus pentachloride in the flask C, and heat the mixture in an oil-bath for hours. Then reverse the condenser as shown in Fig. 67(B), but replace the calcium chloride tube by a tube leading to a water-pump, the neck of the reaction-flask C being closed with a rubber stopper. Now distil off the phosphorus oxychloride under reduced pressure by heating the flask C in an oil-bath initially at 25-30, increasing this temperature ultimately to 110°. Then cool the flask, when the crude 3,5-dinitro-benzoyl chloride will solidify to a brown crystalline mass. Yield, 16 g., i.e,y almost theoretical. Recrystallise from caibon tetrachloride. The chloride is obtained as colourless crystals, m.p. 66-68°, Yield, 13 g Further recrystallisation of small quantities can be performed using petrol (b.p. 40-60°). The chloride is stable almost indefinitely if kept in a calcium chloride desiccator. 

Method 2. Mix 1 0 g. of 3 5-dinitrobenzoic acid with 1 5 g. of phosphorus pentachloride in a small, dry test-tube. Warm the mixture gently over a small smoky fiame to start the reaction when the reaction has subsided (but not before), boil for 1-2 minutes or until the solid matter has dissolved. Pour the mixture while still liquid on a dry watch glass (CAUTION the fumes are irritating to the eyes). When the product has solidified, remove the liquid by-product (phosphorus oxychloride) by transferring the pasty mixture to a pad of several thicknesses of filter paper or to a small piece of porous tile. Spread the material until the liquid has been absorbed and the residual solid is dry. Transfer the 3 5 dinitrobenzoyl chloride to a test-tube, add 0-5-1 ml. of the alcohol, and continue as in Method 1. 

Alkyl phosphates. From phosphorus oxychloride and the alcohol in the presence of p3u-idine, for example ... 

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 ... 

The phosphorus oxychloride formed in the reaction is a dehydrating agent also. 

The liquid phosphorus oxychloride, b.p. 107°, is a by-product and is removed by fractional distillation under normal pressure. Unless the b.p. of the acid chloride differs very considerably (say, <] 100°) from that of the phosphorus oxychloride, the acyl halide is liable to contain traces of the latter. In such circumstances it is preferable to use thionyl chloride for the preparation of the acid chloride. 

Alternatively a mixture of 90 g. of sodium benzenesulphonate and 60 g. (36 ml.) of phosphorus oxychloride may be used. The experimental procedure is identical with that for phosphorus pentachloride, but the yield is slightly better. 

The preparation of 4-methylcoumarin is an example of the Pechmann reaction, which consists in the interaction of a phenol with a 3-ketonic ester In the presence of a condensing agent (sulphuric acid, aluminium chloride, phosphorus oxychloride or pho.sphoric oxide) ... 

Place a mixture of 30 g. of 3 5-dinitrobenzoic acid (Section IV,168 and 33 g. of phosphorus pentachloride in a Claisen flask fit a reflux condenser into the short neck and cork the other neck and side arm (compare Fig. Ill, 31, 1). Heat the mixture in an oil bath at 120-130° for 75 minutes. Allow to cool. Remove the phosphorus oxychloride by distillation under reduced pressure (25°/20 mm.) raise the temperature of the bath to 110°. The residual 3 5-dinitrobenzoyl chloride solidifies on cooling to a brown mass the yield is quantitative. Recrystallise from carbon tetrachloride the yield is 25 g., m.p. 67-68° and this is satisfactory for most purposes. Further recrystallisation from a large volume of light petroleum b.p. 40-60°, gives a perfectly pure product, m.p. 69 -6°. 

Crystal violet is an example of a triphenylmethane dye. Its preparation in the laboratory may be illustrated by the condensation of 4 4 -tetramethyl-diaminobenzophenone (Michler s ketone) and dimethylaiiiliue in the presence of phosphorus oxychloride ... 

In a 1 htre round-bottomed flask, provided with an air condenser, place a mixture of 25 g. (26 ml.) of pure dimethylanihne, 10 g. of Michler s ketone (4 4 tetramethyldiaminobenzophenone) and 10 g. (6 ml.) of phosphorus oxychloride. Heat on a boding water bath for 5 hours. Add about 150 ml. of water and sufificient sodium hydroxide solution to render the solution alkaline. Calculate the quantity of sodium hydroxide required upon the basis of the hydrolysis product derived from the phosphorus oxychloride ... 

The reaction is again most successful with phenol and indole derivatives. Reaction con-litions are also quite mild. Phosphorus oxychloride may be used in refluxing chloroform or ligher boiling hydrocarbons. Duration of the reaction is usually less than 6 hours (T. Kameta-li, 1977 A E.E. van Tamelen, 1969). 

Alkoxy and 2-methyl derivatives of A-2-thiazoline-4-one (182) react with phosphorus oxychloride to yield the thiazolylphosphoric esters (183), which have insecticidal uses (Scheme 95) (428-430). 

Hydroxythiazoles give 2-chIorothiazole derivatives almost quantitatively upon treatment with phosphorus oxychloride (221, 229, 428). This constitutes a convenient synthesis method for these compounds when the conversion of 2-aminothiazoles to 2-chlorothiazole derivatives fails. Esters of thiocarbamic acid or thiourethanes also react with a-halocarbonyl compounds to give the corresponding 2-alkoxythiazoles (50, 68, 209, 272). 

Thiazole carboxamides are readily dehydrated to nitriles in good yields by heating with phosphorus oxychloride (91), phosphorus pentoxide (87, 71), or phosphoryl chloride (16) (Scheme 19). 

Treatment of thiazole-4,5-dicarboxamides (26) with phosphorus oxychloride in the presence of pyridine afforded 4,5-dicyanOthiazoles (27) (Scheme 20) (91). 

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