Tributylphosphine → Ethyl [(4-{[1-(3-bromo-2-methylphenyl)pentyl]oxy}-2-methylphenyl)oxy]acetate

HRID 1391795Notes

Reaction equation

HRID 1391795 reaction equation
[Br:1][C:2]1[C:3]([CH3:14])=[C:4]([CH:8]([OH:13])[CH2:9][CH2:10][CH2:11][CH3:12])[CH:5]=[CH:6][CH:7]=1.O[C:16]1[CH:28]=[CH:27][C:19]([O:20][CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])=[C:18]([CH3:29])[CH:17]=1.C1CCN(C(N=NC(N2CCCCC2)=O)=O)CC1.C(P(CCCC)CCCC)CCC>C1COCC1>[Br:1][C:2]1[C:3]([CH3:14])=[C:4]([CH:8]([O:13][C:16]2[CH:28]=[CH:27][C:19]([O:20][CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])=[C:18]([CH3:29])[CH:17]=2)[CH2:9][CH2:10][CH2:11][CH3:12])[CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 13831TributylphosphineHCID 730421,1'-(Azodicarbonyl)dipiperidineHCID 21986458Ethyl (4-hydroxy-2-methylphenoxy)acetateHCID 586298181-(3-Bromo-2-methylphenyl)-1-pentanol

Product 1

HCID 58629845Ethyl [(4-{[1-(3-bromo-2-methylphenyl)pentyl]oxy}-2-methylphenyl)oxy]acetateYield 57.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 1-(3-bromo-2-methylphenyl)-1-pentanol (495 mg, 1.92 mmol) in anhydrous THF (40 mL) under nitrogen at 0° C. was added portion-wise ethyl (4-hydroxy-2-methylphenoxy)acetate (405 mg, 1.93 mmol), followed by slow addition (over 25 min) of ADDP (971 mg, 3.85 mmol) and drop-wise addition of tributylphosphine (0.96 mL, 3.85 mmol). The resulting mixture was then stirred for 16 h with gradual warming to ambient temperature. The solvent was then removed under vacuum and the residue partitioned between EtOAc (100 mL) and water (150 mL), the layers separated, and the aqueous re-extracted with EtOAc (100 mL). The combined organic layer was then dried (Na2SO4), filtered and reduced under vacuum and the resulting residue purified by SPE (silica, 50 g cartridge), eluting with cyclohexane:EtOAc (gradient 99:1 to 4:1) to afford the title compound as a colourless oil (495 mg).

Workup

  1. customThe solvent was then removed under vacuum
  2. customthe residue partitioned between EtOAc (100 mL) and water (150 mL)
  3. customthe layers separated
  4. extractionthe aqueous re-extracted with EtOAc (100 mL)
  5. dry with materialThe combined organic layer was then dried (Na2SO4)
  6. filtrationfiltered
  7. customthe resulting residue purified by SPE (silica, 50 g cartridge)
  8. washeluting with cyclohexane

Sources & evidence

ORD record
ord-dc0ae2c7e8ea4414bcf2d2c08f902c3a
Source dataset
uspto-grants-2008_03
Patent number
US07338960B2

Reaction notes

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