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

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##

1. temperatureat reflux for 1 hour
2. temperatureThe resulting brick-red mixture is cooled in an ice-water bath
3. stirringthe solution is stirred for 18 hours at room temperature
4. customAfter the 18 hour period, a brown-yellow mixture results
5. washThis mixture is washed with 7 portions of water
6. extractionextracted with dilute hydrochloric acid
7. extractionThe acidic extract which
8. extractionThis gum is extracted with ethyl ether
9. extractionThe ether extract
10. dry with materialis dried over sodium sulfate
11. customto give a gum
12. customThe gum is then chromatographed
13. additiona solvent mixture of benzene-ethanol-ammonium hydroxide (96:4:1/4) as the eluent
14. customto leave an oil
15. extractionThe ethereal extract
16. extractionis then extracted with dilute hydrochloric acid
17. extractionThe acidic extract which
18. extractionextracted with ethyl ether
19. extractionThe ethereal extract
20. washis washed with sodium chloride
21. dry with materialdried over sodium sulfate
22. customto give a gum which
23. customseeding result in the formation of crystals
24. customThese crystals are then recrystallized from ethyl acetate

ORD record

ord-f9006a409a8b4de69b288746f62cd74d

Source dataset

uspto-grants-1978_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04125531