Toluene → Methyl 4-[1-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl)-2-methyl-1-propenyl]benzoate

HRID 129251Notes

Reaction equation

HRID 129251 reaction equation
[I-].[CH:2]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([CH3:4])[CH3:3].C[Si](C)(C)[N-][Si](C)(C)C.[K+].C1(C)C=CC=CC=1.[CH3:41][C:42]1([CH3:66])[CH2:51][CH2:50][C:49]([CH3:53])([CH3:52])[C:48]2[CH:47]=[C:46]([C:54]([C:56]3[CH:65]=[CH:64][C:59]([C:60]([O:62][CH3:63])=[O:61])=[CH:58][CH:57]=3)=O)[CH:45]=[CH:44][C:43]1=2>C1C=CC=CC=1.ClCCl.CCCCCC>[CH3:66][C:42]1([CH3:41])[CH2:51][CH2:50][C:49]([CH3:52])([CH3:53])[C:48]2[CH:47]=[C:46]([C:54]([C:56]3[CH:65]=[CH:64][C:59]([C:60]([O:62][CH3:63])=[O:61])=[CH:58][CH:57]=3)=[C:2]([CH3:4])[CH3:3])[CH:45]=[CH:44][C:43]1=2

Participants

7

Reactant 4

HCID 1140TolueneHCID 2723783Isopropyltriphenylphosphonium iodideHCID 3251421Potassium bis(trimethylsilyl)amideHCID 10784070Methyl 4-[(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthyl)carbonyl]benzoate

Product 1

HCID 10362193Methyl 4-[1-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl)-2-methyl-1-propenyl]benzoateYield 71%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent3×HCID 21226440Methylenechloride HexaneSolvent

Procedure

To a suspension of isopropyltriphenylphosphonium iodide (0.35 g, 0.807 mmol) in 3 mL of benzene under argon at room temperature was added a 0.5M solution of potassium hexamethyldisilazide in toluene (1.8 mL, 0.89 mmol), and the red solution was stirred for 5 min. A solution of keto-ester 3 (0.169 g, 0.481 mmol) in 3 mL of benzene was added, and the red solution was heated to 110° C., while approximately 4 mL of benzene was distilled out. After 1 h, the reaction mixture was diluted with 40% ethyl acetate/hexane and washed with saturated aqueous NaHCO3 and brine. The organic layer was dried over anhydrous MgSO4, filtered through a plug of silica gel, and concentrated to afford a solid. Flash chromatography (40% dichloromethane/hexane) yielded the desired product 19 as a white powder (0.128 g, 71%): Rf 0.44 (50% CH2Cl2 /hexane). The structure of the product was also confirmed using IR, 1H NMR and mass spectroscopy.

Workup

  1. distillationwas distilled out
  2. waitAfter 1 h
  3. additionthe reaction mixture was diluted with 40% ethyl acetate/hexane
  4. washwashed with saturated aqueous NaHCO3 and brine
  5. dry with materialThe organic layer was dried over anhydrous MgSO4
  6. filtrationfiltered through a plug of silica gel
  7. concentrationconcentrated
  8. customto afford a solid

Sources & evidence

ORD record
ord-927ab13649fc4cc191933e2f465f6617
Source dataset
uspto-grants-1995_11
Patent number
US05466861

Reaction notes

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