Boron trifluoride etherate → HCID 584534, compound

HRID 1779414Notes

Reaction equation

HRID 1779414 reaction equation
[C:1]12(O)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.[C:12]([O:18][CH2:19][CH3:20])(=[O:17])[CH2:13][C:14]([CH3:16])=[O:15].B(F)(F)F.CCOCC.[OH-].[K+]>CCCCC.C(OCC)C.O.C(O)(=O)C>[C:1]12([CH:13]([C:14](=[O:15])[CH3:16])[C:12]([O:18][CH2:19][CH3:20])=[O:17])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2

Participants

9

Reactant 4

HCID 8000Boron trifluoride etherate2×HCID 8868Ethyl AcetoacetateHCID 14797Potassium HydroxideHCID 641521-Adamantanol

Product 1

HCID 584534HCID 584534, compoundYield 73.4%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8003PentaneSolvent

Procedure

A stirred solution of 5.0 grams (0.033 mole) of adamantan-1-ol and 4.7 grams (0.036 mole) of ethyl acetoacetate in 60 mL of pentane was cooled to 7° C., and 5.1 grams (0.036 mole) of boron trifluoride etherate was added during a 2 minute period. An additional 3.8 mL of boron trifluoride etherate was then added, also during a 2 minute period. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature, where it was stirred for about 16 hours. After this time, the reaction mixture was again cooled to 7° C., and 24 grams of aqueous 50% potassium hydroxide was added. The reaction mixture was then made acidic with 12 mL of acetic acid. The reaction mixture was poured into a separatory funnel with 50 mL of water and 130 mL of diethyl ether. The mixture was shaken and the layers were separated. The water layer was washed with two portions of 30 mL each of toluene. The toluene washes were combined with the diethyl ether layer, and 100 mL of water was added to the combination. The mixture was filtered and the layers were separated. The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 6.4 grams of ethyl 2-(adamant-1-yl)-3-oxobutanoate. The NMR spectrum was consistent with the proposed structure.

Workup

  1. additionUpon completion of addition
  2. temperatureAfter this time, the reaction mixture was again cooled to 7° C.
  3. stirringThe mixture was shaken
  4. customthe layers were separated
  5. washThe water layer was washed with two portions of 30 mL each of toluene
  6. additionwas added to the combination
  7. filtrationThe mixture was filtered
  8. customthe layers were separated
  9. dry with materialThe organic layer was dried with sodium sulfate
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-b9f6fa9c723347048eeca755fdf7cb26
Source dataset
uspto-grants-1997_05
Patent number
US05627189

Reaction notes

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