Dimethyl Sulfate → (S)-(+)-2-ethynyl-3,4-dihydro-6-methoxy-2,5,7,8-tetramethyl-2H-1-benzopyran

HRID 1722212Notes

Reaction equation

HRID 1722212 reaction equation
[C:1]([C@:3]1([CH3:17])[CH2:8][CH2:7][C:6]2[C:9]([CH3:16])=[C:10]([OH:15])[C:11]([CH3:14])=[C:12]([CH3:13])[C:5]=2[O:4]1)#[CH:2].S(OC)(O[CH3:22])(=O)=O.[OH-].[Na+].[OH-].[NH4+]>CC(C)=O>[C:1]([C@:3]1([CH3:17])[CH2:8][CH2:7][C:6]2[C:9]([CH3:16])=[C:10]([O:15][CH3:22])[C:11]([CH3:14])=[C:12]([CH3:13])[C:5]=2[O:4]1)#[CH:2]

Participants

6

Reactant 4

HCID 6497Dimethyl SulfateHCID 14798Sodium HydroxideHCID 14923Ammonium HydroxideHCID 9859440(S)-2-ethynyl-3,4-dihydro-2,5,7,8-tetramethyl-2H-1-benzopyran-6-ol

Product 1

HCID 14478580(S)-(+)-2-ethynyl-3,4-dihydro-6-methoxy-2,5,7,8-tetramethyl-2H-1-benzopyranYield 47%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

A solution of (S)-(+)-2-ethynyl-3,4-dihydro-2,5,7,8-tetramethyl-2H-1-benzopyran-6-ol (354 mg, 1.54 mmol) in acetone (9 mL) was treated with dimethyl sulfate (0.8 mL), and 50% NaOH (1.2 mL) for 2 h at 25° C. with stirring. Ammonium hydroxide solution (1.0N, 50 mL) was added, and it was extracted with ether (3×50 mL). The extracts were combined, washed with 1.0N HCl, water, and dried over MgSO4. It was filtered and concentrated in vacuo to give 400 mg of solid, which or crystallization from ether-hexane (1:12) afforded 141 mg (47%) of (S)-(+)-2-ethynyl-3,4-dihydro-6-methoxy-2,5,7,8-tetramethyl-2H-1-benzopyran as white prisms: mp 94°-97° C., [α]D25 +53.86°, (C 0.4233, CHCl3).

Workup

  1. extractionit was extracted with ether (3×50 mL)
  2. washwashed with 1.0N HCl, water
  3. dry with materialdried over MgSO4
  4. filtrationIt was filtered
  5. concentrationconcentrated in vacuo
  6. customto give
  7. custom400 mg of solid, which or crystallization from ether-hexane (1:12)

Sources & evidence

ORD record
ord-de441647a72a4dc68998cff18c18b821
Source dataset
uspto-grants-1989_08
Patent number
US04855085

Reaction notes

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