Abstract:The reaction of norbornenone and morpholine without an acid catalyst results in formation of a tricycloenamine, a normal enamine, an enamine reduction product, and an amino ketone. The amino ketone is apparently formed via a homoenolate ion. Treatment of bicyclo[2.2.2] oct-5-en-2-one with morpholine and an acid catalyst gives the thermodynamic product, A'-phenylmorpholine, in refluxing xylene and the kinetic product, 2-Ar-morpholinobicyclo[2.2.2]octa-2,5-diene, at room temperature.
“…Synthesis of exo -2-Aminonorbornanes (3). These amines were produced by heating a mixture of 0.05 mol of the amino ketone, 45 mL of diethylene glycol, 11 g of potassium hydroxide, and 8 mL of 85% hydrazine hydrate at 110 °C for 6 h. The product mixture was steam distilled, the distillate extracted with diethyl ether, and the combined ether extract dried with MgSO 4 . The extract was filtered, solvent removed, and the residual oil distilled.…”
Section: Methodsmentioning
confidence: 99%
“…The norbornane system studied is a series of 2-substituted norbornanes with tertiary amine substituents, these substituents having exo ( 3 ) and endo ( 4 ) configurations. The endo amines ( 4 ) were made by hydride reduction of the corresponding iminium salts in a manner previously reported . Syntheses of the exo amines ( 3 ) were carried out in a manner previously described as shown in Scheme . 1 …”
A series of endo- and exo-norbornylamines were synthesized and their relative basicities determined in acetonitrile and dimethylformamide solvents. The exo isomer is always more basic than the corresponding endo isomer in either solvent. All of the bicyclic amines studied have higher pK(a)'s in acetonitrile solvent than in dimethylformamide except for the 2-morpholinonorbornanes which are just the reverse. This effect is explained by the ability of the morpholine group to disperse a positive charge and the relative polarizabilities of the solvents. Semiempirical AM1 and PM3 methods along with ab initio HF/STO-3G, HF/3-21G, and HF/6-31G methods were used to calculate proton affinities and dipole moments for each of the amines. The results of the theoretical calculations correspond well with the experimental observations.
“…Synthesis of exo -2-Aminonorbornanes (3). These amines were produced by heating a mixture of 0.05 mol of the amino ketone, 45 mL of diethylene glycol, 11 g of potassium hydroxide, and 8 mL of 85% hydrazine hydrate at 110 °C for 6 h. The product mixture was steam distilled, the distillate extracted with diethyl ether, and the combined ether extract dried with MgSO 4 . The extract was filtered, solvent removed, and the residual oil distilled.…”
Section: Methodsmentioning
confidence: 99%
“…The norbornane system studied is a series of 2-substituted norbornanes with tertiary amine substituents, these substituents having exo ( 3 ) and endo ( 4 ) configurations. The endo amines ( 4 ) were made by hydride reduction of the corresponding iminium salts in a manner previously reported . Syntheses of the exo amines ( 3 ) were carried out in a manner previously described as shown in Scheme . 1 …”
A series of endo- and exo-norbornylamines were synthesized and their relative basicities determined in acetonitrile and dimethylformamide solvents. The exo isomer is always more basic than the corresponding endo isomer in either solvent. All of the bicyclic amines studied have higher pK(a)'s in acetonitrile solvent than in dimethylformamide except for the 2-morpholinonorbornanes which are just the reverse. This effect is explained by the ability of the morpholine group to disperse a positive charge and the relative polarizabilities of the solvents. Semiempirical AM1 and PM3 methods along with ab initio HF/STO-3G, HF/3-21G, and HF/6-31G methods were used to calculate proton affinities and dipole moments for each of the amines. The results of the theoretical calculations correspond well with the experimental observations.
“…Direct attack on the carbonyl carbon without ring opening was demonstrated by Cook et al,4 on treating nortricyclanone H 2R2NH + (3) with amine salts rather than with free nucleophilic amines, followed by LiAlH4 reduction (3 -» 7). They have also ob-tained5 ring-retained products from cyclopropanecarboxaldehyde and methyl cyclopropyl ketone in presence of basic and acidic catalysts, respectively.…”
authentic sample. The aqueous layer was acidified (hydrochloric acid) and extracted (ether). Evaporation of ether gave 0.41 g (68%) of diphenylacetic acid (13). Recrystallization of 13 from benzene gave colorless granules, mp 147-148 °C. The melting point and IR spectrum of 13 were in good agreement with those of an authentic sample.
Norbornenon (I) reagiert mit Morpholin (II) in Gegenwart von Säure zum Diamin (III) und zum Enamin (IV), während in Abwesenheit der Säure noch die beiden Amine (V) und (VI) erhalten werden.
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