Chloromethyl Methyl Ether → HCID 18970132, compound

HRID 399156Notes

Reaction equation

HRID 399156 reaction equation
[OH:1][C:2]1[C:7]2[C:8]([CH3:18])=[C:9]([CH2:14][CH2:15][CH2:16][OH:17])[C:10]([CH3:13])([CH3:12])[O:11][C:6]=2[CH:5]=[C:4]([CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[CH:3]=1.[H-].[Na+].[CH3:26][O:27][CH2:28]Cl>CN(C=O)C>[CH3:26][O:27][CH2:28][O:1][C:2]1[C:7]2[C:8]([CH3:18])=[C:9]([CH2:14][CH2:15][CH2:16][OH:17])[C:10]([CH3:12])([CH3:13])[O:11][C:6]=2[CH:5]=[C:4]([CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[CH:3]=1

Participants

5

Reactant 3

HCID 7864Chloromethyl Methyl EtherHCID 24758Sodium hydrideHCID 18970140HCID 18970140, compound

Product 1

HCID 18970132HCID 18970132, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 1.96 g (6.16 mmol) of 5-Hydroxy-2,2,4-trimethyl-7-pentyl-2H-1-benzopyran-3-propanol in 10 mL of anhy. DMF (Aldrich) under argon at RT was added 260 mg (~1.05 eq.) of a 60% dispersion of sodium hydride (Aldrich) and the mixture stirred at RT under argon until effervescence had ceased and the solution had become a clear, darker colored solution. To the stirred solution was added 0.55 mL (~1 eq.) of methoxymethyl chloride (Aldrich, 85% purity technical grade) by syringe directly into the solution with the needle tip below the surface of the solution. The color of the reaction mixture discharged and a precipitate formed within 1 min. Stirring was continued for 0.5 hr. Half of the solution was then withdrawn by syringe for use in another reaction. The remaining half was poured into a mixture of 50 mL of sat. aq. NaHCO3 and 100 mL EtOAc, the mixture shaken well and sufficient water added to dissolve solids that formed to give two clear phases. The phases were separated and the organic phase washed with half-sat. aq. NaCl (2×50 mL), sat. aq. NaCl (1×50 mL), dried (Na2SO4), evaporated under reduced pressure and the residue dried under high vacuum to give 1.05 g (~94%) of the desired product 5-(Methoxymethoxy)-2,2,4-trimethyl-7-pentyl-2H-1-benzopyran-3-propanol as an oil, shown by 1H-NMR to be of good purity.

Workup

  1. customa precipitate formed within 1 min
  2. stirringStirring
  3. customHalf of the solution was then withdrawn by syringe for use in another reaction
  4. additionThe remaining half was poured into a mixture of 50 mL of sat. aq. NaHCO3 and 100 mL EtOAc
  5. stirringthe mixture shaken well
  6. additionsufficient water added
  7. dissolutionto dissolve solids that
  8. customformed
  9. customto give two clear phases
  10. customThe phases were separated
  11. washthe organic phase washed with half-sat
  12. dry with materialaq. NaCl (2×50 mL), sat. aq. NaCl (1×50 mL), dried (Na2SO4)
  13. customevaporated under reduced pressure
  14. customthe residue dried under high vacuum

Sources & evidence

ORD record
ord-8de5d0f182c745f3ad54078088fe191e
Source dataset
uspto-grants-1998_10
Patent number
US05817766

Reaction notes

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