Citric Acid → Diisopropylether methanol

HRID 467055

Reaction equation

HRID 467055 reaction equation
[C:1]([O-:5])([CH3:4])([CH3:3])C.[K+].FCP(C1C=CC=CC=1)(C1C=CC=CC=1)[C:10]1[CH:15]=CC=C[CH:11]=1.F[B-](F)(F)F.C(N(CC)[C:36](N[C@H]1C[C@H]2[C@@H](CC3C4C(=CC=CC2=4)NC=3C=O)N(CCC)C1)=[O:37])C.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>O1CCOCC1>[CH:1]([O:5][CH:10]([CH3:15])[CH3:11])([CH3:4])[CH3:3].[CH3:36][OH:37]

Participants

6

Reactant 4

HCID 311Citric AcidHCID 15067675HCID 15067675, compoundHCID 23665647Potassium tert-butoxideHCID 178506414HCID 178506414, compound

Product 1

HCID 21882575Diisopropylether methanol

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Procedure

1.58 g (14 mmol) of potassium tert-butanolate was added in three portions in 2-3 minute intervals to a suspension of 5.35 g (14 mmol) of fluoromethyl-triphenylphosphine-tetrafluoroborate (Burton, D. J., Wiemers, D. M., J. Fluor. Chem. 27, 85 (1984)) in 120 ml of dry dioxane was instilled. It was allowed to stir for 30 minutes at room temperature and then a solution of 560 mg (1.4 mmol) of 1,1-diethyl-3-(2-formyl-6-n-propyl-8α-ergolinyl)-urea in 15 ml of dioxane was instilled. After 30 minutes (TLC), the batch was poured onto ice and a pH of 3 was padjusted with solid citric acid. It was extracted with ethyl acetate and the organic phase was washed with 2 N citric acid. The combined aqueous phases were made alkaline with 25% NH3 solution with cooling and extracted with dichloromethane. These organic phases were washed with water, dried on MgSO4 and the solvent was removed in a vacuum. After chromatography (prepacked columns C; Merck company, diisopropyl ether/methanol 95:5) a total yield of 279 mg (48%) of fluorovinyl compound was obtained. By crystallization of the individual fractions, both isomers were obtained pure.

Workup

  1. waitAfter 30 minutes (TLC)
  2. additionthe batch was poured onto ice
  3. extractionIt was extracted with ethyl acetate
  4. washthe organic phase was washed with 2 N citric acid
  5. temperaturewith cooling
  6. extractionextracted with dichloromethane
  7. washThese organic phases were washed with water
  8. customdried on MgSO4
  9. customthe solvent was removed in a vacuum

Sources & evidence

ORD record
ord-259c15cba9c5456d914f2c38afa5c49f
Source dataset
uspto-grants-1992_10
Patent number
US05158957

Linked notes

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