N,N,N',N'-Tetramethylethylenediamine → HCID 86736152, compound

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Reaction Steps

To a solution of 2.91 parts of 2-(2,2-diphenylethyl)-1-azabicyclo[2.2.2]octane in 40 parts by volume of cyclohexane is added under a nitrogen atmosphere 5.1 parts by volume of 2.17 M solution of butyl lithium in hexane and 1.15 parts of TMEDA. This solution is then stirred at reflux for 1 hour. The resulting brick-red mixture is cooled in an ice-water bath. Then 1.64 parts of bromocyclopentane is added and the solution is stirred for 18 hours at room temperature. After the 18 hour period, a brown-yellow mixture results. This mixture is washed with 7 portions of water and extracted with dilute hydrochloric acid. The acidic extract which contains a small amount of solid is basified with aqueous sodium hydroxide resulting in the formation of a gum. This gum is extracted with ethyl ether. The ether extract is dried over sodium sulfate and then stripped in vacuo to give a gum. The gum is then chromatographed using neutral silica gel as the column absorbent and a solvent mixture of benzene-ethanol-ammonium hydroxide (96:4:1/4) as the eluent. The desired fractions from the chromatography are combined and stripped in vacuo to leave an oil. This oil is dissolved in ethyl ether. The ethereal extract is then extracted with dilute hydrochloric acid. The acidic extract which contains a fine solid is basified with aqueous sodium hydroxide and extracted with ethyl ether. The ethereal extract is washed with sodium chloride, dried over sodium sulfate, and stripped in vacuo to give a gum which is 2-(2-cyclopentyl-2,2-diphenylethyl)-1-azabicyclo[2.2.2]octane. 1.40 Parts of this gum and 0.460 parts of maleic acid are dissolved in 5 parts of methanol. Diluting this solution with 10 parts of ether and seeding result in the formation of crystals. These crystals are then recrystallized from ethyl acetate to give 2-(2-cyclopentyl-2,2-diphenylethyl)-1-azabicyclo[2.2.2]octane (Z)-2-butenedioate (1:1). This compound melts at about 196°-198° C. and is represented by the following formula ##STR13##

Provenance & Evidence