Anhydrous magnesium dichloride

Solid catalyst [Mg-Ti] was analyzed for its composition and specific surface area (Table 2). A 3.0 wt. % of titanium is incorporated on active support. BET surface area of crystalline magnesium dichloride is found to be 10 mVg. The treatment of magnesium dichloride with 2-ethyl-1-hexanol and DBPh followed by diphenyldichlorosilane gives a product [Mg-Ti I] with improved surface area characteristics (50 mVg). The reaction of [Mg-Ti I] with titanium tetrachloride increases the surface area to 115 m /g. These results show that the present process of catalyst synthesis gives approximately tenfold improvement in the surface area of the Mg-Ti catalyst as compared to the starting anhydrous magnesium dichloride. 

During the addition the temperature is maintained at 28-31° (Note 3) by cooling the flask, as needed, by a stream of tap water. The solution is allowed to stand overnight and is then treated with 800 ml. of water to dissolve the precipitated quinoline hydrochloride (Note 4). The mixture is shaken well in a separatory funnel the organic layer is separated and washed with two 200-ml. portions of water and three or four 200-ml. portions of 5% hydrochloric acid. After the extract has dried over anhydrous magnesium sulfate for 5 hours, the solvent is removed by distillation, a water aspirator being used to remove the last portions of the methylene dichloride. Distillation of the residue from a 1-1. Claisen flask by means of an air bath maintained at 125-135° gives 460-495 g. (71-76%) (Note 5) of a colorless oil, b.p. 74-78° (0.5 mm.), 24d 1.4832. This product is sufficiently pure for use in the preparation below. 

Diorgano Tellurium5 (Thiourea Dioxide Method) A mixture of 2 mmol of the diorgano tellurium dichloride and 10 ml of 2 molar aqueous sodium hydroxide solution is stirred for 15 min at 20°. Then, 0.432 g (4 mmol) thiourea dioxide and 10 m/ petroleum ether (30-60°) are added. The mixture is stirred at 20° until it becomes clear. The phases are separated. The aqueous phase is extracted three times with diethyl ether. The combined organic phases are dried with anhydrous magnesium sulfate, the dried mixture is filtered, and the solvent evaporated from the filtrate. The residue is placed on a silica-gel column. The product is eluted with petroleum ether. 

Decomposition of Hcxadecyl Phenyl Tellurium Dichloride in DMF7 A stirred suspension of0.2g (0.40 mmol) hexadecyl phenyl tellurium dichloride, 30 mg (0.51 mmol) of sodium chloride, and 2 ml of DMF is heated under nitrogen at 100° for 1 h. The mixture is Ihen allowed to cool to20 J, is poured into water, and extracted with hexane. The extract is dried with anhydrous magnesium sulfate and filtered through a short column of silica gel. The solvent is evaporated to leave l-chlorohexadecune as a colorless oil yield 96 mg (92%). 

Oxotelluraxanthcnc2 180 mg of 9-oxotelluraxanthene Te, 7e-dichloride are suspended in 10 m/ of diethyl ether, and the suspension is shaken in a separatory funnel with a solution of 240 mg (1.9 mmol) of sodium sulfite and 180 mg (1.3 mmol) of potassium carbonate in 5 ml of water until the suspended solid has dissolved. The organic phase is separated, the aqueous phase is extracted twice with diethyl ether, the organic phases are combined, washed with water, dried with anhydrous magnesium sulfate, filtered, and the solvent evaporated under aspirator vacuum. The residue is recrystallized from bcnzene/dichloromethane yield 120 mg (82%) m.p. 116°. 

Dimethyl-2-oxo-l-butyl 4-Methoxyphenyl Tellurium Dichloride A suspension of 1.02 g (3.0 mmol) of 4-methoxyphenyl tellurium trichloride in 10 m/ benzene is mixed with 0.516 g (3.0 mmol) 3,3-dimethyl-2-trimethylsiloxybut-l-ene. The mixture is refluxed for 10 h, then treated with 100 ml methanol/water (1 1), and extracted with chloroform. The organic phase is separated, dried with anhydrous magnesium sulfate, filtered, and the filtrate evaporated. The residue is chromatographed on silica gel with chloroform as the mobile phase. The product is recrystallized from chloroform/petroleum ether (30-60°) yield 80% m.p. 90-92°. 

A solution of the monosodium salt of diacetylene in 300 ml of liquid ammonia is prepared from 13.8 g (0.6 g-atoms) sodium and 24.6 g (0.2 moles) l,4-dichlorobut-2-yne. To this mixture is added a suspension of 5 g (17.6 mmoles) 3-methoxyestra-l,3,5(10)-trien-17-one in anhydrous tetrahydrofuran at —40° and the reaction mixture is stirred and maintained at this temperature for 2 hr. Ammonium chloride is then added and the ammonia is allowed to evaporate overnight. The residual solids are extracted with methylene dichloride and the extracts washed with water, dried over magnesium sulfate, and evaporated at 70°. The resultant dark gum is... 

To a well stirred suspension of 9 g of sodium phenyl acetate and 2.4 g of magnesium turnings in 25 cc of anhydrous ether, a solution of 9.4 cc of isopropyl bromide in 50 cc of anhydrous ether are added. The mixture is refluxed for one hour (during which time propane is evolved) and then 5 cc of cyclopentanone in 25 cc of anhydrous ether are added dropwise. The mixture is then refluxed for one hour and poured over ice water containing some hydrochloric acid. The ether solution is separated and extracted with 200 cc of 5% sodium hydroxide. The alkaline solution on acidification gives the free acid which is filtered off, dried in a desiccator and recrystallized from a mixture of ethylene dichloride and petroleum ether. 

Its oxidising character plays a role in all other reactions. Surprisingly, it is thought to form explosive dichlorine oxide with chlorine. It leads to a and very exothermic reaction with disulphur dichloride and detonations with metals potassium, K-Na alloy, magnesium with phosphorus and anhydrous or hydrated hydrazine. 

Cobalt, iron and nickel yield black precipitates when hydrogen is passed through suspensions of their respective anhydrous dichlorides mixed with phenyl magnesium bromide in dry ether ... 

Ethyl 2-diazo-3-oxo-4,4,4-trifluorobutyrate 634 A solution of trifluorvacetic anhydride (131g) in methylene dichloride (75 ml) is dropped, during 1 h, into a stirred solution of ethyl diazoacetate (73.5 g) and pure, anhydrous pyridine (51 g) in methylene dichloride (100 ml). The precipitated pyridinium trifluoroacetate is filtered off and the filtrate is washed with sodium carbonate solution and then with an oxalic acid solution and dried over magnesium sulfate. Subsequent fractionation in a vacuum affords the product (109 g 83%), b.p. 75-77°/10 mm. 

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