Water → 1-(3-Fluorophenyl)-4-methoxymethylenecyclohexane

HRID 1929256Notes

Reaction equation

HRID 1929256 reaction equation
[Cl-].[CH3:2][O:3][CH2:4][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CC(C)([O-])C.[K+].[F:30][C:31]1[CH:32]=[C:33]([CH:37]2[CH2:42][CH2:41][C:40](=O)[CH2:39][CH2:38]2)[CH:34]=[CH:35][CH:36]=1.O>C1COCC1.C1(C)C=CC=CC=1>[F:30][C:31]1[CH:32]=[C:33]([CH:37]2[CH2:42][CH2:41][C:40](=[CH:2][O:3][CH3:4])[CH2:39][CH2:38]2)[CH:34]=[CH:35][CH:36]=1

Participants

7

Reactant 4

HCID 962WaterHCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 189531424-(3-Fluorophenyl)cyclohexanoneHCID 23665647Potassium tert-butoxide

Product 1

HCID 579969431-(3-Fluorophenyl)-4-methoxymethylenecyclohexaneYield 93.7%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-30 °C

Procedure

Well-dried methoxymethyltriphenylphosphonium chloride (112.1 g) and THF (1000 ml) were mixed under a nitrogen atmosphere, and cooled to −30° C. Then, potassium t-butoxide (t-BuOK; 36.7 g) was put in thereto in twice in the temperature range of −30° C. to 20° C. After the mixture had been stirred at −20° C. for 30 minutes, the compound (35) (41.9 g) dissolved in THF (200 ml) was added dropwise thereto in the temperature range of −30° C. to −20° C. After the reaction had been stirred at −10° C. for 30 minutes, it was poured into a mixture of water (500 ml) and toluene (500 ml), and mixed. The mixture was then allowed to stand until it had separated into two phases of organic and aqueous phases, and an extractive operation was carried out. The organic phase obtained was fractionated, washed with water, and then dried over anhydrous magnesium sulfate. The solution obtained was concentrated under reduced pressure, and the residue obtained was purified with a fractional operation by means of column chromatography using toluene as the eluent and silica gel as the stationary phase powder. The eluent obtained was concentrated under reduced pressure, giving 45.0 g of 1-(3-fluorophenyl)-4-methoxymethylenecyclohexane (36). The yield based on the compound (35) was 93.7%.

Workup

  1. customtwice in the temperature range of −30° C. to 20° C
  2. additionwas added dropwise
  3. customin the temperature range of −30° C. to −20° C
  4. stirringAfter the reaction had been stirred at −10° C. for 30 minutes
  5. additionmixed
  6. customhad separated into two phases of organic and aqueous phases
  7. customThe organic phase obtained
  8. washwashed with water
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customThe solution obtained
  11. concentrationwas concentrated under reduced pressure
  12. customthe residue obtained
  13. customwas purified with a fractional operation by means of column chromatography
  14. customThe eluent obtained
  15. concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record
ord-a687abd53ce2486e8692a66ac0b3a43d
Source dataset
uspto-grants-2012_05
Patent number
US08187494B2

Reaction notes

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