Magnesium phenyl- bromide

Triphenyl-carbinol, (C6H5)3COHy from Ethyl Benzoate and Phenyl Magnesium Bromide. (Grignard Reaction 6 (a).)... 

Phenylthiazolo[2.3-e]tetrazole treated with equimolecular amounts of phenyl magnesium bromide gives phenyl(4-phenyl-2-thiazoiyl)triazene (334) (Scheme 191) (620). 

It should be noted that Grignard reagents obtained from 2-methylthiazole do not yield acetyl derivatives (31). Ketones can also be obtained from cyanothiazoles and Grignard reagents (87). Thus phenyl magnesium bromide and 5-cyanothiazole give phenyl 5-thiazolyl ketone (Scheme 35). 

The formation of diphenyl on oxidation of phenyl magnesium bromide by anhydrous ferric chloride has been known for some... 

Chloro-5,6-diphenyl-as-triazine readily undergoes methoxy-de-chlorination at 25° (< 12 hr) with methanolic methoxide and at 65° (4.5 hr) in non-basified methanol. The chloro group is also displaced by hydrazine (80°, 1 hr), ammonia (140°, 6 hr), and phenyl-magnesium bromide (70°, 12 hr), the latter forming the triphenyl compound 315.3-Chloro-6-phenyl-as-triazine is unstable to cold water or alkali and to hot alcohol or aqueous potassium carbonate. ... 

The substitution of the lone proton on the benzhydryl carbon by a methyl group again affords compounds with antihistamine activity. Reaction of an appropriate acetophenone (21) with phenyl-magnesium bromide affords the desired tertiary alcohols (22). 

Reaction of substituted nitrile with phenyl magnesium bromide gives, after hydrolysis, the benzophenone Re-... 

Aj Preparation of (2-Amino-5-ChlorophenyljPhenylmethaneimine (4356 CB) A solution of 228.7 g (1.5 mols) of 2-amino-5-chlorobenzonitrile in 1,800 ml of dry ether is added slowly in the course of about 3.5 hours to a solution of phenyl magnesium bromide prepared from 109 g (4.5 g-atoms) of magnesium turnings and 848 g (5.4 mols) of bromobenzene In 3,600 ml of anhydrous ether, and the mixture then heated under reflux for 15 hours. 

The manufacture of the cyclohexyl analog is as follows. Phenyl magnesium bromide was prepared from 48.5 g (0.308 mol) of bromobenzene, 7 g (0,29 mol) of magnesium, and 125 ml of dry ether. To it was added at 5°C over a period of A hour 40 g (0.18 mol) of cyclohexyl (3-(N-piperidyl)-ethyl ketone (BP 115° to 117°C/1 mm) in 125 ml of dry ether. The mixture was allowed slowly to come to room temperature, refluxed for one hour, and then poured into ice containing 80 ml of concentrated hydrochloric acid. Ammonium chloride (100 g) and 200 ml of concentrated ammonium hydroxide were added and the organic layer was separated. After drying and removing the solvent, the residue was distilled under reduced pressure. The base distilled at 158° to 170°C (1 mm) and solidified. Upon recrystallization from methanol it melted at 112° to 113°C. 

The residue was dissolved in 75 ml of tetrahydrofuran, treated with charcoal, and sodium sulfate and filtered. This solution was added to a solution in 250 ml of tetrahydrofuran of phenyl magnesium bromide prepared from 17.7 ml (0.17 mol) of bromobenzene. This mixture was stirred and heated under reflux for 1 hour. It was then cooled and diluted with 400 ml of ether and sufficient 3N hydrochloric acid to make it acidic. The aqueous phase was separated, adjusted to pH 8 with 3N sodium hydroxide and extracted 3 times with 200 ml of ether. The ether extracts were combined, washed with water and dried over sodium sulfate. The residue left on removal of the ether in vacuo was crystallized from petroleum ether to give 3.3 g of 7-chloro-2,3-dihvdro-1-methyl-5-phenvl-1 H-1,4-benzodiazepine, according to U.S. Patent 3,624,703. 

The starting material is prepared by the reaction of acetophenone, paraformaldehyde and pyrrolidine to give OJ-pyrrolidinopropiophenone. That is in turn reacted with phenyl magnesium bromide to give 1,1-diphenyl-3-pyrrolidinpropan-1-ol. 

C,HjMgBr + C.HsCOOQH — (C6H ),COMgBr + MgBrOC Hj Phenyl magnesium bromide Ethyl benzoate... 

A 500-ml. three-necked round-bottomed flask is fitted with an efficient reflux condenser, a glycerol-sealed mechanical stirrer,1 a dropping funnel, and a gas inlet tube extending nearly to the blades of the stirrer (Note 1). An absorption train,2 with the addition in / of a safety tube which extends nearly to the bottom, is connected to the upper end of the reflux condenser (Note 2). A 2-cm. layer of water in J allows it to serve as a bubble counter K is one-third filled with a 50% potassium hydroxide solution. The entire apparatus is set up in subdued light in a hood and swept with dry hydrogen (Notes 3 and 4). Phenyl-magnesium bromide is prepared in the flask by the usual procedure 3 from 78.5 g. (0.5 mole) of bromobenzene, 12 g. (0.5 gram... 

Available from Pierce Chemical Co., Rockford, Illinois. The ketone can also be prepared conveniently from phenyl-magnesium bromide and trifluoroacetic acid by the method of Dishart and Levine.2... 

Phenyl Magnesium Bromide Phenylpropanolamine Phosphorus Oxychloride Piperidine... 

The action of a Grignard reagent, e.g. phenyl magnesium bromide, on methyl fluoroacetate gives among other products PhaCH CH(OH)Ph and desoxybenzoin.1... 

The action of phenyl magnesium bromide on ethyl 2-fluoroethoxypropionate gave, not the expected diphenyl-2-2 -fluoroethoxyethylcarbinol, but rather surprisingly the corresponding bromo compound (p. 160).2... 

Finally, nitrosobenzene reacts with Grignard reagents. With phenyl-magnesium bromide, in the usual way there is produced diphenyl-hydroxylamine, an exceptionally reactive substance ... 

Michler s ketone is converted into the carbinol base of malachite green by the action of phenyl magnesium bromide (the Grignard reaction)... 

An ethereal solution of phenyl magnesium bromide is prepared 1 Blaise, Compt. rend., 1901, 133, 1217. 

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