tert-Butyl bromoacetate → Tert-butyl 3-hydroxy-3-[2-(8-phenyloctyl)phenyl]propionate

HRID 1885287Notes

Reaction equation

HRID 1885287 reaction equation
[Cl-].C([Al+]CC)C.Br[CH2:8][C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10].[C:16]1([CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][C:30]2[CH:37]=[CH:36][CH:35]=[CH:34][C:31]=2[CH:32]=[O:33])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>CCCCCC.O1CCCC1.[Zn].[Cu]Br>[OH:33][CH:32]([C:31]1[CH:34]=[CH:35][CH:36]=[CH:37][C:30]=1[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)[CH2:8][C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10]

Participants

8

Reactant 3

HCID 79177tert-Butyl bromoacetateHCID 98176132-(8-Phenyloctyl)benzaldehydeHCID 16686102Diethyl aluminum chloride

Product 1

HCID 15617420Tert-butyl 3-hydroxy-3-[2-(8-phenyloctyl)phenyl]propionate

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 24593copper(I) bromideCatalystHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-20 °C

Procedure

A solution of diethylaluminum chloride (0.0082 moles, 8.2 ml) in hexane was added to a slurry of zinc dust (0.0111 mol; 0.7248 g) and a catalytic amount of copper (I) bromide (0.0004 moll; 0.0585 g) in anhydrous tetrahydrofuran (40 ml) while stirring under argon at 20° C. The resulting mixture was then cooled to -20° C. in an ice-methanol bath. A solution of t-butyl bromoacetate (0.0082 mol; 1.32 ml) and 2-(8-henyloctyl)benzaldehyde of Example 5(a) or (b) (0.0082 moles; 2.3969 g) in anhydrous tetrahydrofuran was added slowly over 60 min. The reaction was stirred overnight and was permitted to warm up slowly to room temperature. The mixture was filtered to remove zinc, concentrated, and azeotroped with methylene chloride. The resulting oil was then chromatographed on silica using 5% ethyl acetate in hexane with 0.5% formic acid to yield the desired product.

Workup

  1. temperatureto warm up slowly to room temperature
  2. filtrationThe mixture was filtered
  3. customto remove zinc
  4. concentrationconcentrated
  5. customazeotroped with methylene chloride
  6. customThe resulting oil was then chromatographed on silica using 5% ethyl acetate in hexane with 0.5% formic acid

Sources & evidence

ORD record
ord-63d38da647ff4596b0f4e05559182ac2
Source dataset
uspto-grants-1992_09
Patent number
US05143931

Reaction notes

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