Cyclohexanone—continued

Dicyclohexylarnine may be selectively generated by reductive alkylation of cyclohexylamine by cyclohexanone (15). Stated batch reaction conditions are specifically 0.05—2.0% Pd or Pt catalyst, which is reusable, pressures of 400—700 kPa (55—100 psi), and temperatures of 75—100°C to give complete reduction in 4 h. Continuous vapor-phase amination selective to dicyclohexylarnine is claimed for cyclohexanone (16) or mixed cyclohexanone plus cyclohexanol (17) feeds. Conditions are 5—15 s contact time of <1 1 ammonia ketone, - 3 1 hydrogen ketone at 260°C over nickel on kieselguhr. With mixed feed the preferred conditions over a mixed copper chromite plus nickel catalyst are 18-s contact time at 250 °C with ammonia alkyl = 0.6 1 and hydrogen alkyl = 1 1. 

Cyalohexylideneaaetonit ri-le. A 1-L three-necked, round-bottomed flask equipped with a reflux condenser, mechanical stirrer and addition funnel, is charged with potassium hydroxide (855 pellets, 33.0 g, 0.5 mol. Note 1) and acetonitrile (250 ml. Notes 2 and 3). The mixture is brought to reflux and a solution of cyclohexanone (49 g, 0.5 mol. Note 4) in acetonitrile (100 mL) is added over a period of 0.5-1.0 hr. Heating at reflux is continued for 2 hr (Note 5) after the addition is complete and the hot solution is then poured onto cracked ice (600 gl. The resulting binary mixture is separated... 

The reaction is carried out in a manner similar to that described above (Chapter 11, Section II). In a 250-ml flask fitted with stirrer, condenser, and dropping funnel is placed a solution of 19.25 g (0.0505 mole) of the phosphonium salt in 180 ml of THF. The nitrogen atmosphere is established and 0.05 mole of phenyllithium added (as a solution in benzene, available from Foote Mineral Co.). The mixture is stirred for 45 minutes at room temperature and then refluxed for 15 minutes. To the red-brown solution is added dropwise over 20 minutes 4.91 g (0.05 mole) of distilled cyclohexanone stirring is continued for 24 hours. The mixture is then concentrated by distillation at... 

FIGURE 1 Continuous process for the manufacture of e-caprolactone by oxidation of cyclohexanone with peracetic acid. 

In a 2-1. wide-necked Erlenmeyer flask are mixed 66.2 g. (0.525 mole) of 2-(hydroxymethylene)cyclohexanone (Note 1), 400 ml. of methylene chloride, and 106 g. (1.05 moles) of triethylamine (Note 2). The flask is cooled in an ice-salt bath at —12 to —15°, and 98.0 g. (0.500 mole) of p-toluenesulfonyl azide (Note 3) is added with vigorous mechanical stirring over a period of approximately 1 hour, at such a rate that the temperature of the reaction mixture does not rise above —5°. Stirring is continued for an additional 2 hours as the cooling bath melts. A solution of 30.8 g. (0.55 mole) of potassium hydroxide in 400 ml. of water is added, and the mixture is stirred for 15 minutes at room temperature. The resulting emulsion is placed in a 2-1. separatory funnel, the methylene chloride layer is separated after the emulsion has broken, and the aqueous alcoholic layer is... 

In a 2-1. three-necked flask (Note 1), fitted with a dropping funnel, condenser (equipped with a Drierite tube), and efficient stirrer driven by a powerful motor, is placed a mixture of 600 ml. of benzene, 48 g. (0.85 mole) of potassium hydroxide (Note 2), and 76.4 g. of powdered calcium carbide (Note 3). While this mixture is being stirred vigorously, 85 g. (0.87 mole) of cyclohexanone is added over a period of 0.5-1 hour. The mixture is dark gray and will become warm, but no external cooling is necessary. Stirring is continued, and within 24 hours the contents congeal (Note 4). This semisolid is allowed to stand for an additional 4 days (Note 5). 

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