Pentachloride tetrachlorides

Niobium pentachloride-tetrachloride equilibrium 42 Niobium-alkali metal chloride complexes 1... 

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. 

Other catalysts which may be used in the Friedel - Crafts alkylation reaction include ferric chloride, antimony pentachloride, zirconium tetrachloride, boron trifluoride, zinc chloride and hydrogen fluoride but these are generally not so effective in academic laboratories. The alkylating agents include alkyl halides, alcohols and olefines. 

Method 2. Place 90 g. of sodium benzenesulphonate (Section IV,29) (previously dried at 130-140° for 3 hours) and 50 g. of powdered phosphorus pentachloride (1) in a 500 ml. round-bottomed flask furnished with a reflux condenser heat the mixture in an oil bath at 170-180° for 12-15 hours. Every 3 hours remove the flask from the oil bath, allow to cool for 15-20 minutes, stopper and shake thoroughly until the mass becomes pasty. At the end of the heating period, allow the reaction mixture to cool. Pour on to 1 kilo of crushed ice. Extract the crude benzenesulphonyl chloride with 150 ml. of carbon tetrachloride and the aqueous layer with 75 ml. of the same solvent. Remove the solvent under atmospheric pressure and proceed as in Method 1. The yield is about 170 g., but depends upon the purity of the original sodium benzenesulphonate. 

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°. 

Acetaldehyde reacts with phosphoms pentachloride to produce 1,1-dichloroethane [75-34-3] and with hypochlorite and hypoiodite to yield chloroform [67-66-3] and iodoform [75-47-8], respectively. Phosgene [75-44-5] is produced by the reaction of carbon tetrachloride with acetaldehyde in the presence of anhydrous aluminum chloride (75). Chloroform reacts with acetaldehyde in the presence of potassium hydroxide and sodium amide to form l,l,l-trichloro-2-propanol [7789-89-1] (76). 

Acid Chloride Formation. Monoacid chlorides of maleic and fumaric acid are not known. Treatment of maleic anhydride or maleic acid with various reagents such as phosgene [75-44-5] (qv), phthaloyl chloride [88-95-9] phosphoms pentachloride [10026-13-8] or thionyl chloride [7719-09-7] gives 5,5-dichloro-2(5JT)furanone [133565-92-1] (4) (26). Similar conditions convert fumaric acid to fumaryl chloride [627-63-4] (5) (26,27). NoncycHc maleyl chloride [22542-53-6] (6) forms in 11% yield at 220°C in the reaction of one mole of maleic anhydride with six moles of carbon tetrachloride [56-23-5] over an activated carbon [7440-44-4] catalyst (28). 

Manufacture. Phosphoms pentachloride is manufactured by either batch or continuous processing. In the former, the phosphoms trichloride usually dissolves in carbon tetrachloride before being treated with chlorine. A mixture of ca one part of phosphoms trichloride to one part of carbon tetrachloride is introduced to a water-jacketed vessel that contains an efficient stirrer and a tight cover with a redux condenser. The chlorine is passed into the vessel below the Hquid level, and crystals of phosphoms pentachloride form in the Hquid. When the reaction is completed, the suspension of crystals of phosphoms pentachloride in the carbon tetrachloride is drawn out of the vessel and the crystals are filtered and then dried by circulating hot water through the jacket of the filter. The clarified carbon tetrachloride is returned to the reaction vessel. 

Zirconium tetrachloride forms additional compounds with phosphoms pentachloride ZtCl PCl and ZtCl 2PC1. However, the alleged... 

Chromyl azide chloride Molybdenum azide pentachloride Molybdenum azide tetrachloride Silver azide chloride Tin azide trichloride Titanium azide trichloride Tungsten azide pentabromide Uranium azide pentachloride Vanadium azide dichloride Vanadyl azide tetrachloride... 

Carbon tetrachloride is used to produce chlorofluorocarbons by the reaction with hydrogen fluoride using an antimony pentachloride (SbCls) catalyst ... 

Polychlorination processes have included exhaustive chlorination in the presence of antimony pentachloride, which destroyed the molecule (1882JCS412). Chlorine in carbon tetrachloride gave 3,4,6,8-tetrachlo-roquinoline chlorine dissolved in thionyl chloride gave the 4,5,7,8-isomer, whereas thionyl chloride alone produced a mixture of 3,4,5,6,7,8-hexachloro- (57%) and 3,4,6,8-tetrachloro- (37%) quinolines (73YZ73 74S356, 74URP432143). 

Phosphorus Pentachloride (Phosphoric chloride, Phosphorus perchloride). PC15, mw 208.27 white to pale yel, fuming, deliq, cryst mass pungent, unpleasant odor mp (under press) 148° ordinarily sublimes without melting at 160—165°. Sol with decompn and liberation of much heat in w or ale sol in C disulfide or tetrachloride. Can be prepd by the action of chlorine on P or P trichloride (Refs 9 10)... 

A suspension of 100 g (0 48 mole, 33% excess) of phosphorus pentachloride in 800 ml of carbon tetrachloride is prepared in a 1-1 flask equipped with an efficient stirrer and an exit valve for the hydrogen chloride that is evolved ( ote 1) Tropilidene (cycloheptatriene, 24.2 g of 91% mateiial, 0.24 mole) (Note 2)... 

Ans. (a) Carbon monoxide, (b) sulfur dioxide, (c) sulfur trioxidc, (d) carbon tetrachloride, (e) phosphorus pentachloride, and (/) sulfur hexafluoride. 

MRH Bromine 1.21/91, carbon tetrachloride 2.89/83, chlorine 3.85/82 Silane burns in contact with bromine, chlorine or covalent chlorides (carbonyl chloride, antimony pentachloride, tin(IV) chloride, etc.) [1], Extreme caution is necessary when handling silane in systems with halogenated compounds, as a trace of free halogen may cause violent explosions [2],... 

Triphenylchloromethane has been made by the action of phosphorus pentachloride,1 hydrogen chloride,2 or acetyl chloride3 upon triphenylcarbinol. It has also been made by the reaction between carbon tetrachloride and benzene in the presence of alumi-... 

Oleoyl chloride has been prepared by treatment of oleic acid with thionyl chloride,3 phosphorus trichloride or pentachloride, and oxalyl chloride.4 The highest yield (86%) reported was secured by use of oxalyl chloride in carbon tetrachloride, but the more economical phosphorus trichloride gave a yield of 60%. The standard procedures for obtaining aliphatic acid chlorides have been described many times without inclusion of details other than physical properties. Only references to the procedures useful in the laboratory are given. 

An older, equally interesting industrial route involves condensing 2-aminoan-thraquinone in nitrobenzene in the presence of antimony pentachloride or titanium tetrachloride. Complex 97 prevents any undesirable formation of anthrim-ide (98). 

Amino(trihalomethyl)methylenemalonates (1539) were chlorinated with chlorine in carbon tetrachloride, with /m-butyl hypochlorite in benzene, and phosphorus pentachloride or /V,/V-dichlorobenzenesulfonamide in dichloroethane (68ZOR1710 75ZOB873). Depending on the molar ratio, A-mono- or JV,./V-dichloro derivatives (1540, R2 = H, Cl) were obtained. 

Silver difluoride, 0014 Silver fluoride, 0013 Sodium chloride, 4036 Sodium iodide, 4623 Tantalum pentachloride, 4185 Tellurium tetrabromide, 0296 Thallium, 4922 Tin(II) chloride, 4116 Tin(IV) chloride, 4174 Tin(II) fluoride, 4331 Titanium(II) chloride, 4117 Titanium dibromide, 0284 Titanium diiodide, 4630 Titanium tetrachloride, 4176 Titanium tetraiodide, 4638 Titanium trichloride, 4158... 

Oki and his co-workers (177) also found that these halogenated compounds (107) exhibited enormous differences in reactivity when they were treated with Lewis acids. The sc form undergoes a Friedel-Crafts type cyclization in the presence of titanium tetrachloride, which is a weak Lewis acid, whereas the ap form survives these conditions. The latter reacts in the presence of the stronger Lewis acid antimony pentachloride. This difference is apparently caused by a chloro group in proximity to the site where a cationic center develops during the reaction (Scheme 12). 

Carbon tetrachloride is made by the reaction of carbon disulfide and chlorine in the presence of a catalyst, such as iron or antimony pentachloride ... 

The pentachloride may be obtained from the tetrachloride, M0CI4. The latter, when heated in a sealed tube sublimes, and upon cooling, disproportion-... 

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