Magnesium diphenyl

Only one aryl compound is knowm, namely, magnesium diphenyl, formed by heating magnesium powder and mercury diphenyl at 200° C. in an atmosphere of nitrogen. Like the alkyl compounds, it is readily oxidisable in air and decomposed by water. 

CUCI2 on phenyl magnesium halides also provide reasonable quantities of diphenyl. Uses include its action as a fungistat during shipment of apples and oranges, and as a heat transfer agent (dowtherms) mixed with diphenyl ether and terphenyls. 

Propiophenone. Prepare a solution of diphenyl-cadmium in 110 ml. of dry benzene using 4 9 g. of magnesium, 32 4 g. of bromobenzene and 19 5 g. of anhydrous cadmium chloride. Cool the solution to 10°, and add during 3 minutes a solution of 14 -8 g. of propionyl chloride (b.p. 78-79°) in 30 ml. of dry benzene use external coohng with an ice bath to prevent the temperature from rising above 40°. Stir the mixture for 2 hours at 25-35°. Work up the product as detailed above except that 6 per cent, sodium carbonate solution should replace the saturated sodium bicarbonate solution. The yield of propiophenone, b.p. 100-102°/16 mm., is 17 6 g. 

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 parent system 3 was reported fw the first time as a product obtained in low yield originating from the vapor-phase cyclodehydrogenaticMi of /V,/V -diphenyl-m-phenylenediamine (137) over a platinum-on-magnesium catalyst (Scheme 17) (61JOC1509). 

A chiral magnesium catalyst prepared from magnesium iodide and 1,2-diphenyl-ethylenediamine was also found to he effective in asymmetric aza Diels-Alder reaction of a-imino ester 21b with 7a (Scheme 5.12) [32]. The novel catalyst was discovered using parallel comhinatorial methods. 

Diphenylacetonitrile is condensed with 2dimethyl-amino)-2,2-diphenyl valeronitrile. It is then reacted with ethyl magnesium bromide and then hydrolyzed using HCl to give methadone hydrochloride. 

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. 

Propanol with magnesium in reduction of chlorobenzene, 47, 104 Propionyl fluoride, 46, 6 n Propylamine, 46, 85 n Propylhydrazine, 46, 85 C ( Propyl) N phenylmtrone, genera tion from phenylhydroxylamme and n butyraldehyde, 46, 97 Purification of tetrahydrofuran (Warning), 46,105 4H Pyran 4-one, 2 6 dimethyl 3,5 diphenyl, 47, 54... 

In this connection it may be of interest to mention that a wide variety of reagents such as the fatty acid salts of Cu11, Mn, Co, Ni, and Al, and magnesium acetylacetonate were reported to have no effect upon the rate of decomposition of w-octadecyl azidoformate in diphenyl ether solution 58>. 

Catalytic properties of external chiral additives such as (2S,3/ )-4-dimethyl-amino-l,2-diphenyl-3- methyl-2-butoxide (A 16) (574, 575) and 2-magnesium-3-zinc salts of dialkyl (f ,f )-tartrate (A17) were employed in the highly stereoselective addition of organozinc reagents to derivatives of 3,4-dihydro-isoquinoline-A-oxide (Scheme 2.147) (576). 

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 ... 

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