Allyl bromide → HCID 86617396, compound

HRID 2076589Notes

Reaction equation

HRID 2076589 reaction equation
O.[C:2]1(C)C=CC(S(O)(=O)=O)=C[CH:3]=1.C[O:14][CH:15](OC)[C:16]1[C:40]([O:41][CH2:42]OC)=[C:39]([C:45]([F:48])([F:47])[F:46])[CH:38]=[CH:37][C:17]=1[CH2:18][O:19][C:20]1[CH:25]=[CH:24][C:23]([C:26]2[CH:31]=[CH:30][C:29]([CH2:32][C:33]([O:35][CH3:36])=[O:34])=[CH:28][CH:27]=2)=[CH:22][CH:21]=1.C(=O)([O-])[O-].[K+].[K+].C(Br)C=C>CC(C)=O.CN(C)C=O.O>[CH2:42]([O:41][C:40]1[C:16]([CH:15]=[O:14])=[C:17]([CH:37]=[CH:38][C:39]=1[C:45]([F:46])([F:47])[F:48])[CH2:18][O:19][C:20]1[CH:21]=[CH:22][C:23]([C:26]2[CH:27]=[CH:28][C:29]([CH2:32][C:33]([O:35][CH3:36])=[O:34])=[CH:30][CH:31]=2)=[CH:24][CH:25]=1)[CH:2]=[CH2:3]

Participants

8

Reactant 4

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 86617395Methyl (4'-{[2-(dimethoxymethyl)-3-(methoxymethoxy)-4-(trifluoromethyl)benzyl]oxy}-1,1'-biphenyl-4-yl)acetate

Product 1

HCID 86617396HCID 86617396, compoundYield 84%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent

Procedure

After p-toluenesulfonic acid monohydrate (1.01 g, 5.31 mmol) was added to a solution of methyl (4′-{[2-(dimethoxymethyl)-3-(methoxymethoxy)-4-(trifluoromethyl)benzyl]oxy}-1,1′-biphenyl-4-yl)acetate (2.38 g, 4.45 mmol) obtained in Example (6-7) in acetone (14 ml), the mixture was stirred at room temperature for 14 hours. After the reaction mixture was poured into water and the mixture was extracted with ethyl acetate, 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. Potassium carbonate (738 mg, 5.34 mmol) and allyl bromide (0.462 ml, 5.34 mmol) were successively added to a solution of the obtained residue in N,N-dimethylformamide (4 ml) and the mixture was stirred at 50° C. for 2 hours. After the reaction mixture was poured into water and the mixture was extracted with ethyl acetate, 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=50/1-2/1) to give methyl (4′-{[3-(allyloxy)-2-formyl-4-(trifluoromethyl)benzyl]oxy}-1,1′-biphenyl-4-yl)acetate (1.81 g, yield: 84%).

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  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 50° C. for 2 hours
  7. extractionthe mixture was extracted with ethyl acetate
  8. washthe organic layer was 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=50/1-2/1)

Sources & evidence

ORD record
ord-919d50fe785b46a69c2e9a3366eee52d
Source dataset
uspto-grants-2011_04
Patent number
US07923573B2

Reaction notes

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