Dimethylformamide → 3,3'-[Butane-1,4-diylbis(oxymethylene)]bis(3-methyloxetane)

HRID 1376677Notes

Reaction equation

HRID 1376677 reaction equation
[H-].[Na+].[CH2:3]([OH:8])[CH2:4][CH2:5][CH2:6][OH:7].[H][H].[C:11]1([CH3:21])[CH:16]=CC(S(O)(=O)=O)=C[CH:12]=1.O[CH2:23][C:24]1([CH3:28])[CH2:27][O:26][CH2:25]1.CN([CH:32]=[O:33])C>>[CH3:23][C:24]1([CH2:28][O:7][CH2:6][CH2:5][CH2:4][CH2:3][O:8][CH2:12][C:11]2([CH3:21])[CH2:32][O:33][CH2:16]2)[CH2:27][O:26][CH2:25]1

Participants

6

Reactant 5

HCID 6228Dimethylformamide2×HCID 80641,4-ButanediolHCID 24758Sodium hydrideHCID 71332124HCID 71332124, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 144346323,3'-[Butane-1,4-diylbis(oxymethylene)]bis(3-methyloxetane)Yield 84%

Conditions

Temperature
100 °C

Procedure

Sodium hydride (50% dispersion in mineral oil, 29.25 g, 0.609 mol) was washed twice with hexanes and was suspended in 350 mL of DMF. Then, butane-1,4-diol (26.15 g, 0.290 mol) was added dropwise over 20 min while hydrogen gas was evolved and a beige solid precipitated. The mixture was stirred for 30 min and a solution of 3-hydroxymethyl-3-methyloxetane p-toluenesulfonate (148.58 g, 0.58 mol) in 200 mL of DMF was added. The mixture was heated to 60° C. for 24 h and 100° C. for 6 h when 1H NMR analysis of an aliquot showed that the starting sulfonate had been consumed. The mixture was poured into 600 mL of water and extracted with three portions of 200 mL of methylene chloride. The combined organic extracts were washed with three portions of 200 mL of water, dried over magnesium sulfate, and evaporated to give 66.5 g, representing an 84% yield of 1,4-bis-[(3-methyl-3-oxetanyl)methyloxy]-butane as an oil containing DMF (4%). The oil was purified by bulb-to-bulb distillation at 130° C. and 0.1-mm of pressure to give 60.74 g, representing a 76.7% yield, of analytically pure ether.

Workup

  1. customa beige solid precipitated
  2. customhad been consumed
  3. additionThe mixture was poured into 600 mL of water
  4. extractionextracted with three portions of 200 mL of methylene chloride
  5. washThe combined organic extracts were washed with three portions of 200 mL of water
  6. dry with materialdried over magnesium sulfate
  7. customevaporated
  8. customto give 66.5 g

Sources & evidence

ORD record
ord-b8c52e1ff21c480badc387f6f4ee89ed
Source dataset
uspto-grants-1997_09
Patent number
US05663289

Reaction notes

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