A 2-l., two-necked, round-bottomed flask fitted with a mechanical stirrer and a reflux condenser is charged with 40.0 g. (0.232 mole) of 4-cyanobenzenesulfonamide, 600 ml. of 75% (v/v) formic acid, and 40 g. of Raney nickel alloy. The stirred mixture is heated under reflux for 1 hour. The mixture is filtered with suction through a Büchner funnel coated with a filter aid, and the residue is washed with two 160-ml. portions of 95% ethanol. The combined filtrates are evaporated with a rotary evaporator. The solid residue is dissolved in 400 ml. of boiling water and freed from a small amount of insoluble material by decantation through a plug of glass wool placed in a filter funnel. The filtrate is chilled in an ice bath, and the precipitate is collected by filtration with suction, washed with a small amount of cold water, and dried at 50° under vacuum, yielding about 32 g. of crude product, m.p. 112–114°.

     The product is dissolved in 800 ml. of hot 95% ethanol, 15.5 g. of activated carbon is added, and the mixture is swirled periodically while it is allowed to cool for 1 hour. The activated carbon is removed by filtration with suction through a bed of filter aid, the filter cake is washed with 50 ml. of 95% ethanol, and the combined filtrates are evaporated with a rotary evaporator. The residue is dissolved in 225 ml. of boiling water, and the hot solution is decanted through glass wool placed in a filter funnel. The filtrate is cooled to 0°, the product is collected by filtration with suction, washed with a small amount of cold water, and dried in a vacuum oven at 50°, yielding 25.6–28.0 g. (62.9–68.8%) of 4-formylbenzenesulfonamide, m.p. 117–118°.

       To a flusk are added 57 g (0.3 mol) of stannous chloride and 200 ml of dry ether. The mixture is saturated with dry hygrogen chloride until it separates into two layers. The lower layer consists of stannous chloride dissolved in ethereal hydrogen chloride. Octanenitrile, 25g (0.18 mol) is added dropwise with vigorous stirring and after a few minutes the aldimine stannichloride begins to separate out of solution. The reduction is substantially completed after 2 h. The aldehyde is formed by hydrolysis of the aldimine complex with warm water and isolated by steam distillation or extraction with ether. The aldehyde is redistilled to yield a colorless liquid, bp 65℃ (11mm).

     In a 1-liter flask equipped with a stirrer, condenser, dropping funnel, and thermometer is placed 10.2 g (0.3 mol) of lithium aluminum hydride in 300 ml of ether. The flask contains a nitrogen atmosphere throughout the reaction period. To the stirred solution is added 39.6 g (0.45 mol) of ethyl acetate over a period of 1.25 h at 3-7℃. The reaction mixture is stirred for an additional 0.5 h and then 24.9 g (0.30 mol) of trimethylacetonitrile is added over a period of 5 min. The temperature rise to 10℃, with the formation of a highly visous solution. The reaction mixture is stirred for 1 h at 0℃ and then the solution is decomposed cautiously with 300 ml of 5 N H 2 SO 4 . The ether layer is seperated and the layer is extracted three times with 50 ml portions of ether. The ether extracts are washed with saturated

sodium bicarbonate solution followed by ether washings with 30 ml portions of cold water in order to remove ethanol. The ether extracts are dried over sodium sulfate and distilled to yield 25.8 g (74%) of pivalaldehyde, bp 70-72.5℃ (747 mm), n 20 D 1.3794.

    To a flask containing 0.11 mol of methyl magnesium iodide (prepared from 7 ml of methyl iodide in 30 ml of ether containing 2.7 g of magnesium) is added 25 ml of benzene followed by 15 g (0.074 mol) of 9-cyanophenanthrene. The reaction mixture is refluxed for 3 h, cooled, and hydrolyzed with cold ammonium chloride solution. The benzene-ether layer is separated, shaken with cold dilute hydrochloric acid, and then refluxed for 1 h in order to hydrolyze the ketimine hydrochloride to the ketone. The ketone, which precipitates as an oil, is seperated, distilled under pressure, and then recrystallized from ethanol to yield 9.5 g (58%), mp 73-74℃.