Cyclohexanone, condensation with morpholine

Monofekphthalic acid, 42, 77 Morpholine, condensation with cyclohexanone, 41, 65... 

This triethanolamine procedure was used also in a synthesis of docosanedioiC acid starting with the condensation of cyclohexanone with morpholine to form 1 morpholino-1-cyclohexene (1), and acylation of this enamine with sebacoyl chlorid ... 

A 250-ml round-bottom flask is charged with a mixture of cyclohexanone (14.7 g, 0.15 mole), morpholine (15.7 g, 0.18 mole), and / -toluenesulfonic acid monohydrate (0.15 g) in 50 ml of toluene. The flask is fitted with a water separator and a condenser and is brought to reflux (mantle). The separation of water begins immediately and the theoretical amount (2.7 ml) is obtained in about 1 hour. Without further treatment, the reaction mixture may then be distilled. After removal of the toluene at atmospheric pressure, the product is obtained by distillation at reduced pressure, bp II8-I207IO mm, 1.5122-1.5129, in about 75% yield. 

To a 500 ml, three-necked, round-bottomed flask equipped with a Dean and Stark trap, condenser, and stirrer is added a mixture of 52.5 gm (0.60 mole) of morpholine, 49 gm (0.5 mole) of cyclohexanone, 100 ml of toluene, and 0.5 gm ofp-toluenesulfonic acid. The contents are refluxed for approximately 4 hr to remove the water of reaction. The product mixture is cooled and then distilled to afford 59 gm (71 %) of the enamine, b.p. 117°-120°C (10 mm), n 5 1.5122-1.5129. Yields of enamine have been reported to vary from 71 to 80%. 

The reaction of NO with the double bonds of enamines also produces compounds containing the diazeniumdiolate functional group bound to carbon, and some of the compounds prepared in this way have the potential to serve as spontaneous NO donors [43]. The compounds chosen for study were enamines 1-4 derived from condensation of cyclopentanone or cyclohexanone with morpholine or pyrrolidine. When these enamines were dissolved in acetonitrile and treated with NO gas (5-atm pressure) at room temperature, a vigorous exothermic reaction resulted, accompanied by high uptake of NO and formation of a brown precipitate. Attempts to isolate the solid precipitates often resulted in rapid decomposition, with the release of large volumes of gaseous NO. At -78 °C in diethyl ether, the reaction of 4-(l-cyclohexen-l-yl) morpholine (IX) afforded a good yield of crystalline NO addition product (X) ... 

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