Sodium benzophenone

Benzophenone-5 (2-hydroxy-4-methoxy-5-sulfonyl benzophenone sodium salt)... 

U.S. Patent 2,409,754 (1946) to H. R. Henze, Parke-Davis and Co. involves reacting benzophenone, potassium cyanide and ammonium carbonate in 60% ethanol. It can also be prepared by reacting benzophenone, sodium cyanide and ammonium bicarbonate according to Scheme 1. 

It is important that the THF used in the still should not be too wet unless freshly opened commercial dry THF is used, it should be predried with, for example, anhydrous magnesium sulfate followed by sodium wire. The predried THF is placed in flask A, together with benzophenone. Sodium or, better, potassium chips are added. When any initial effervescence has subsided, the flask is heated, and refluxing THF is returned to flask A via the three-way tap B. When the THF is dry, the... 

Dioxane is freshly distilled from a benzophenone-sodium mixture, or, as is more convenient for routine analysis, is used without further purification when obtained as an analytical grade reagent. 

Calcium hydride Sodium/benzophenone Sodium/benzophenone Calcium hydride Magnesium/iodine Calcium hydride or sodium Calcium hydride or sodium Calcium hydride... 

Materials. Samples of the benzophenone salts of the structures (1-5) (Table I) were supplied by Ward-Blenkinsop and Company Limited, Widnes, Cheshire, UK and patent cover is pending. The chemical names of the salts are as follows (1) 4-(3-N,N,N-trimethylammonium-propoxy )benzophenone methylsulphonium salt (2) 4-(2-hydroxy-3-N,N,N-trimethylammoniumpropoxy)benzophenone chloro salt (3) sodium (4-benzoyl)phenylmethylsulphonate (4) 4-(3-sulphoniumpropoxy)benzophenone sodium salt and (5) 4-(2-hydroxy-3-sulphoniumpropoxy)benzo-phenone sodium salt. 

Preparation by treatment of 3 -fluoro-2-hydroxy-5-methyl-benzophenone sodium salt with bromine... 

Materials. Poly(ethylene glycol) diisocyanate with PEG molecular weight 3,400 and M /M = 1.03 was obtained from Shearwater Polymers and was stored at -10°C under nitrogen atmosphere prior to use. Triethylamine, 3,5-dihydroxybenzylalcohol, 18-crown-6 and l,l,l-tris(4-hydroxyphenyl) ethane -all from Aldrich a- bromo-p-tolunitrile, LiAlH4 and K2CO3 from ACROS (Fisher Scientific), were used without further purification. Dichloromethane and tetrahydrofuran (THF) were dried over P2O5 and benzophenone-sodium, respectively, and distilled immediately before use. 

Iodoform reaction. To 0 5 ml. of acetone add 3 ml. of 10% KI solution and 10 ml. of freshly prepared sodium hypochlorite solution and mix well. A pale yellow precipitate of iodofonn is rapidly formed without heating. Acetophenone similarly gives iodoform, but the mixture must be shaken vigorously on account of the limited solubility of acetophenone in water. Benzophenone does not give iodoform. 

Benzophenone. To o 5g.of benzophenone add 1 g. of naphthalene (as a solvent) and heat until completely molten. Add a small piece of sodium and heat again. The surface of the sodium becomes green, and the colour [which is that of the free radical, (C H5),C-ONa] spreads throughout the molten mass on strong heating. 

Bfflizophenone condenses with hydroxylamine hydrochloride in the presence of excess of sodium hydroxide solution to 3deld benzophenone oxime, m.p. 142° ... 

Method 2. Into a 500 ml. round-bottomed flask place 120 ml. of dry A.R. benzene, and 35 g. (29 ml.) of redistilled benzoyl chloride. Weigh out 30 g. of finely-powdered, anhydrous aluminium chloride into a dry corked test-tube, and add the solid, with frequent shaking, during 10 minutes to the contents of the flask. Fit a reflux condenser to the flask, and heat on a water bath for 3 hours or until hydrogen chloride is no longer evolved. Pour the contents of the flask wliile still warm into a mixture of 200 g. of crushed ice and 100 ml. of concentrated hydrochloric acid. Separate the upper benzene layer (filter first, if necessary), wash it with 50 ml. of 5 per cent, sodium hydroxide solution, then with water, and dry with anhydrous magnesium sulphate. Isolate the benzophenone as in Method 1. The yield is 30 g. 

In a 700 ml. bolt-head flask, equipped with a reflux condenser and a mechanical stirrer, place 50 g. of benzophenone (Section IV,139), 500 ml. of rectified spirit, 50 g. of sodium hydroxide and 50 g. of zinc powder. Stir... 

The condensation of aldehydes and ketones with succinic esters in the presence of sodium ethoxide is known as the Stobbe condensation. The reaction with sodium ethoxide is comparatively slow and a httlo reduction of the ketonic compound to the carbinol usually occurs a shorter reaction time and a better yield is generally obtained with the more powerful condensing agent potassium ieri.-butoxide or with sodium hydride. Thus benzophenone condenses with diethyl succinate in the presence of potassium [Pg.919]

Cyanopyiidine (15) reacts with ketones not beating an a-hydiogen in the presence of sodium metal to afford a tertiary alcohol (a precursor of azacydonol) in high yield, eg, the reaction of (15) and benzophenone yields the tertiary benzyl alcohol [1620-30-0] (23) ... 

Reagents, such as tri alkyl aluminums (90) and sodium benzophenone (109), are quite useful as reducing agents. Alkyl aluminums have been used to synthesize Cr(CO), Mo(CO), and W(CO) in high yields (90). In one case, hydrogen was used effectively as a reducing agent in petroleum ether solvent (110,111). 

Dimethyl carbonate is available from Aldrich Chemical Company, Inc. The checkers dried the tetrahydrofuran Immediately before use by distillation from the sodium ketyl of benzophenone under a nitrogen atmosphere. The submitters purchased sodium hydride (50% oil dispersion) from Alfa Products, Morton/Thiokol, Inc. The checkers used 12.24 g of a 50% dispersion of sodium hydride in mineral oil obtained from the same supplier. The dispersion was washed with three portions of pentane to remove the mineral oil and the remaining sodium hydride was allowed to dry under nitrogen. 

Diethyl ether was dried by the submitters by refluxing over lithium aluminum hydride and was distilled immediately before use. The checkers distilled diethyl ether from the sodium ketyl of benzophenone before use. 

Ethyl ether is freshly distilled from sodium/benzophenone ketyl at atmospheric pressure under nitrogen. 

Ether was distilled from sodium ketyl of benzophenone. The dissolution of n-butyllithium in ether was slightly exothermic. 

Tetrahydrofuran was distilled from sodium ketyl of benzophenone. 

Commercially available anhydrous diethyl ether is distilled under nitrogen from a solution of the sodium benzophenone radical anion generated by treating a solution of 10 g of benzophenone and 1 L of ether with 10 g of sodium ribbon until a dark blue or purple color persists. 

Diphenylmethane has been prepared with aluminum chloride as a catalyst from methylene chloride and benzene, from chloroform and benzene as a by-product in the preparation of triphenylmethane, and from benzyl chloride and benzene. It has been prepared by the reduction of benzophenone with hydriodic acid and phosphorus, or with sodium and alcohol. It has also been made by heating a solution of benzyl chloride in benzene with zinc dust, or with zinc chloride. The above method is only a slight modification of the original method of Hirst and Cohen. ... 

Dry benzene was obtained by doubly distilling high purity benzene from a soln containing the blue ketyl formed by the reaction of sodium-potassium alloy with a small amount of benzophenone. 

Two classes of charged radicals derived from ketones have been well studied. Ketyls are radical anions formed by one-electron reduction of carbonyl compounds. The formation of the benzophenone radical anion by reduction with sodium metal is an example. This radical anion is deep blue in color and is veiy reactive toward both oxygen and protons. Many detailed studies on the structure and spectral properties of this and related radical anions have been carried out. A common chemical reaction of the ketyl radicals is coupling to form a diamagnetic dianion. This occurs reversibly for simple aromatic ketyls. The dimerization is promoted by protonation of one or both of the ketyls because the electrostatic repulsion is then removed. The coupling process leads to reductive dimerization of carbonyl compounds, a reaction that will be discussed in detail in Section 5.5.3 of Part B. 

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