Hydrochloric Acid → HCID 67119033, compound

HRID 2076600Notes

Reaction equation

HRID 2076600 reaction equation
Cl([O-])=O.[Na+].O.P([O-])(O)(O)=O.[Na+].[CH2:12]([O:15][C:16]1[C:17]([CH:48]=[O:49])=[C:18]([CH:41]=[CH:42][C:43]=1[C:44]([F:47])([F:46])[F:45])[CH2:19][O:20][C:21]1[CH:26]=[CH:25][C:24]([C:27]2[CH:32]=[CH:31][C:30]([CH2:33][C:34]([O:36][CH2:37][CH:38]=[CH2:39])=[O:35])=[C:29]([F:40])[CH:28]=2)=[CH:23][CH:22]=1)[CH:13]=[CH2:14].[CH3:50][C:51](=[CH:53]C)[CH3:52].S([O-])([O-])(=[O:57])=S.[Na+].[Na+].Cl.CC(C)=C.S(=O)(=O)(O)O.C(=O)([O-])O.[Na+]>C(O)(C)(C)C.C(Cl)Cl.O1CCOCC1>[CH2:12]([O:15][C:16]1[C:43]([C:44]([F:46])([F:47])[F:45])=[CH:42][CH:41]=[C:18]([CH2:19][O:20][C:21]2[CH:22]=[CH:23][C:24]([C:27]3[CH:32]=[CH:31][C:30]([CH2:33][C:34]([O:36][CH2:37][CH:38]=[CH2:39])=[O:35])=[C:29]([F:40])[CH:28]=3)=[CH:25][CH:26]=2)[C:17]=1[C:48]([O:57][C:51]([CH3:53])([CH3:52])[CH3:50])=[O:49])[CH:13]=[CH2:14]

Participants

13

Reactant 9

HCID 313Hydrochloric AcidHCID 1118Sulfuric AcidHCID 8255IsobutyleneHCID 105532-Methyl-2-buteneHCID 24477Sodium ThiosulfateHCID 516892Sodium BicarbonateHCID 516949Sodium Phosphate, Monobasic, MonohydrateHCID 23668197Sodium ChloriteHCID 86617400HCID 86617400, compound

Product 1

HCID 67119033HCID 67119033, compoundYield 83%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 6386tert-ButanolSolventHCID 312751,4-DioxaneSolvent

Procedure

After an aqueous solution (22 ml) of sodium chlorite (2.6 g, 29 mmol) and sodium dihydrogenphosphate monohydrate (2.6 g, 19 mmol) was added dropwise to a solution of allyl (4′-{[3-(allyloxy)-2-formyl-4-(trifluoromethyl)benzyl]oxy}-3-fluoro-1,1′-biphenyl-4-yl)acetate (2.52 g, 4.8 mmol) obtained in Example (11-5) in a mixture of tert-butyl alcohol (51 ml), 1,4-dioxane (17 ml) and 2-methyl-2-butene (17 ml), the mixture was stirred at room temperature for 90 minutes. After a 5% aqueous sodium thiosulfate solution was added to the reaction mixture, the mixture was poured into 1N hydrochloric acid and the mixture was extracted with ethyl acetate (twice). The organic layer was successively washed with water and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. The solvent was removed under reduced pressure to give a residue. Methylene chloride (50 ml), 2-methyl-1-propene (150 ml) and sulfuric acid (1 ml) were successively added to the obtained residue and the mixture was stirred at room temperature overnight. After the reaction mixture was poured into a 5% aqueous sodium hydrogencarbonate solution and the mixture was extracted with ethyl acetate (twice), the organic layer was successively washed with water and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. The residue obtained by removing the solvent under reduced pressure was purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=10/1-3/1) to give tert-butyl 2-(allyloxy)-6-{[(4′-{[(allyloxy)carbonyl]methyl}-3′-fluoro-1,1′-biphenyl-4-yl}oxy]methyl)-3-(trifluoromethyl)benzoate as a colorless powder (2.38 g, yield: 83%).

Workup

  1. extractionthe mixture was extracted with ethyl acetate (twice)
  2. washThe organic layer was successively washed with water
  3. dry with materiala saturated aqueous NaCl solution and dried with anhydrous sodium sulfate
  4. customThe solvent was removed under reduced pressure
  5. customto give a residue
  6. stirringthe mixture was stirred at room temperature overnight
  7. extractionthe mixture was extracted with ethyl acetate (twice), the organic layer
  8. washwas successively washed with water
  9. dry with materiala saturated aqueous NaCl solution and dried with anhydrous sodium sulfate
  10. customThe residue obtained
  11. customby removing the solvent under reduced pressure
  12. customwas purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=10/1-3/1)

Sources & evidence

ORD record
ord-4a16495fcdb34855b78d373404790f20
Source dataset
uspto-grants-2011_04
Patent number
US07923573B2

Reaction notes

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