Hydrochloric Acid → HCID 68447659, compound

HRID 2220573Notes

Reaction equation

HRID 2220573 reaction equation
[CH3:1]C(C)([O-])C.[K+].[CH2:7]([O:9][C:10]1[CH:24]=[CH:23][C:13]2[CH:14]3[CH2:20][CH2:19][CH:18]([CH:21]=O)[CH2:17][CH:15]3[O:16][C:12]=2[C:11]=1[F:25])[CH3:8].O.Cl>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH2:7]([O:9][C:10]1[CH:24]=[CH:23][C:13]2[CH:14]3[CH2:20][CH2:19][CH:18]([CH:21]=[CH2:1])[CH2:17][CH:15]3[O:16][C:12]=2[C:11]=1[F:25])[CH3:8]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 23665647Potassium tert-butoxideHCID 72483450HCID 72483450, compound

Product 1

HCID 68447659HCID 68447659, compound

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

5.0 g (14.0 mmol) of methyltriphenylphosphonium bromide are initially introduced in 50 ml of THF, and 1.60 g (14.3 mmol) of potassium tert-butoxide in 20 ml of THF are added at −5° C. After 1 h at this temperature, 3.40 g (12.9 mmol) of (±)-(3R*, 4aR*, 9bS*)-7-ethoxy-6-fluoro-1,2,3,4,4a,9b-hexahydrodibenzofuran-3-carbaldehyde as a solution in 30 ml of THF are added dropwise, and the batch is stirred at room temperature for 16 h. The reaction solution is hydrolysed using water and acidified using 2 N HCl. The mixture is extracted with MTBE, and the combined organic phases are washed with sat. sodium chloride solution and dried using sodium sulfate. The crude product remaining after removal of the solvents is purified by column chromatography (SiO2, toluene). Further purification was carried out by repeated recrystallisation from isopropanol, giving (±)-(3R*, 4aR*, 9bS*)-7-ethoxy-6-fluoro-3-vinyl-1,2,3,4,4a,9b-hexahydrodibenzofuran as colourless solid (melting point 141° C.).

Workup

  1. extractionThe mixture is extracted with MTBE
  2. washthe combined organic phases are washed with sat. sodium chloride solution
  3. customdried
  4. customafter removal of the solvents
  5. customis purified by column chromatography (SiO2, toluene)
  6. customFurther purification
  7. customrecrystallisation from isopropanol

Sources & evidence

ORD record
ord-0fbede74761747aabe55a0017b1369f2
Source dataset
uspto-grants-2008_08
Patent number
US07417157B2

Reaction notes

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