Acetonitrile → Pentanenitrile, 4,4-dimethyl-3-oxo-

To 2.5 l of liquid ammonia containing 2.5 g of anhydrous ferric chloride was cautiously added 132 g of sodium metal portionwise while keeping the temperature of the reaction mixture at -50° C. To this portion was added rapidly a solution of 234 g of acetonitrile diluted with 300 ml of anhydrous diethyl ether followed by the controlled addition of a solution of 332 g methyl pivaloate diluted with 300 ml anhydrous ether at such a rate that the reaction temperature did not exceed -30° C. Allowed reaction to warm up to room temperature overnight. After all of the ammonia has evaporated off, 1 kg of crushed ice is added followed by enough cold water to make the final volume 4.5 l. The mixture is stirred for 30 min., then filtered through a celite bed. The celite was washed well with cold water and 1 l of 1:1 ether/hexane. The phases were separated, discarding the organic layer. The aqueous layer was cautiously acidified with conc. HCl, cooling as necessary to keep the temperature below 35° C. The acidified aqueous phase was extracted with dichloromethane (3×500 ml). The combined organic phases were dried over MgSO4, filtered, and the solvent removed to yield 316 g of the desired product, M.P. 68° C.

1. customat -50° C
2. customdid not exceed -30° C
3. customAllowed reaction
4. customAfter all of the ammonia has evaporated off
5. addition1 kg of crushed ice is added
6. filtrationfiltered through a celite bed
7. washThe celite was washed well with cold water and 1 l of 1:1 ether/hexane
8. customThe phases were separated
9. temperaturecooling as necessary
10. customthe temperature below 35° C
11. extractionThe acidified aqueous phase was extracted with dichloromethane (3×500 ml)
12. dry with materialThe combined organic phases were dried over MgSO4
13. filtrationfiltered
14. customthe solvent removed

ORD record

ord-343f4c91895947ea82737e57f4657723

Source dataset

uspto-grants-1988_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04781750