Grignard solution prepared from

A solution of 85.8 g (0.2 moles) of 3/ -acetoxy-27-norchoIest-5-en-25-one in 500 ml of anhydrous thiophen-free benzene is added to a Grignard solution prepared from 24.3 g (1 g-atom) of magnesium and 149 g (1.05 moles) of freshly distilled methyl iodide in 575 ml of anhydrous ether. The mixture is refluxed for 3 hr and allowed to stand overnight. After cooling to 5° the complex is decomposed by the slow addition of 200 ml of ice water and 400 ml of 50% acetic acid solution, and steam distilled until no more oil passes over. The residual product is filtered, washed with water and dried at 80°. Crystallization from methanol gives 70 g (87%) of cholest-5-ene-3)5,25-diol mp 179.5-181°. The analytical sample melts at 181.5-182.5° [a]o —39° (CHCI3). 

A) Preparation of p-Hydroxy-p -Methoxybemhydrylidenecyclohexane To a Grignard solution prepared from 110 g of magnesium (4.5 mols) and 840 g of p-bromoanisole (4.5 mols) in one liter of anhydrous ether, there was added dropwise with vigorous agitation 307 g of p-hydroxyphenyl cyclohexyl ketone (1.5 mols) dissolved in one liter of anhydrous ether. Upon completion of the addition the reaction mixture was refluxed for 2.5 hours with agitation, and was then cooled. Thereupon 15 mols of ammonium chloride dissolved in 3 liters of water were added. The ethereal layer was separated, washed with water, dried over anhydrous sodium sulfate and distilled. Yield 370 g. BP 180° to 190°C at 0.1 mm. The substance was recrystallized from a mixture of carbon tetrachloride and petroleum ether. MP 145° to 146°C. 

Grignard solution (prepared from 53 g bromtoluene and 7.2 g magnesium in 300 ml of ether)... 

The Grignard solution (prepared from 53 g bromtoluene and 7.2 g magnesium in 300 ml of ether) was added dropwise to a solution of 35 g p-dimethylaminopropiophenone in 50 ml ether. The mixture was refluxed for 3 hours. Then the liquid phase was added to 500 parts of ice and 100 parts concentrated hydrochloric acid. l-Phenyl-l-p-tolyl-3-dimethylaminopropanol-l was crystallized. M.P. of hydrochloride of l-phenyl-l-p-tolyl-3-dimethylaminopropanol-1 185°C. 

Tris[2-thienyl] Telluronium Bromide3 2.2 g (4.8 mmol) of bis[2-thienyl] tellurium dibromide are added to a Grignard solution prepared from 1.7 g (10 mmol) of 2-bromothiophene in 50 ml of diethyl ether. The mixture is heated under reflux for 2 h, cooled, added to 15 ml of water, and filtered. The filter cake is washed with water and dried in a vacuum dessicator. The dry product is extracted with a large volume of methanol and the product precipitated by concentration of the extract m.p. 244° (253° corrected). 

Contrary to what had been observed for the reaction of the two methylmagnesium species in the reaction of the Grignard solution prepared from bromomethane and magnesium with 2-methylbenzophenone [27], the LANA reactions of the two methylmagnesium species do, indeed, have different results, such that the overall outcome of the reaction is determined by the position of the Schlenk equilibrium. 

The simplest technique is to drop a solution of iodine (less than the calculated amount) in dry ether into an ethereal Grignard solution prepared from the aryl bromide (ca. 1 mole) and magnesium. When the iodine color has disappeared and subsequent reaction is ended, the mixture is treated with ice-water and dilute hydrochloric acid. The ethereal layer contains unchanged aryl bromide and aromatic hydrocarbon as well as aryl iodide and is worked up by any suitable method.845... 

Ethyldiphenylphosphine oxide 397 Diphenylphosphinic acid (0.22 g) is converted into the acid chloride by 1-2 hours boiling under reflux with thionyl chloride (0.5 ml) in toluene. About half the solvent is then distilled off and the residual solution is diluted with benzene and dropped at room temperature into a Grignard solution prepared from magnesium (0.25 g) and ethyl bromide (2.5 ml). The reaction is complete after half an hour s boiling under reflux. The product is hydrolysed by ice and hydrochloric acid, the aqueous layer is washed with ether, and ether phases are united, dried, and evaporated. The residue is subjected to steam-distillation and then extracted several times with ether. The residue left on evaporation of these extracts crystallizes at once or on short storage and is decolorized in acetone by charcoal. Recrystallization from ether-light petroleum or aqueous acetone affords the oxide, m.p. 123-124° (67%). 

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