Sodium hydride → Tetrakis-[(3-methyl-3-oxetanyl)methoxymethyl]methane

HRID 1376675Notes

Reaction equation

HRID 1376675 reaction equation
[H-].[Na+].[OH:3][CH2:4][C:5]1([CH3:9])[CH2:8][O:7][CH2:6]1.[H][H].Br[CH2:13][C:14]([CH2:19]Br)([CH2:17]Br)[CH2:15]Br>CN(C=O)C>[CH3:9][C:5]1([CH2:4][O:3][CH2:13][C:14]([CH2:19][O:3][CH2:4][C:5]2([CH3:9])[CH2:8][O:7][CH2:6]2)([CH2:17][O:3][CH2:4][C:5]2([CH3:9])[CH2:8][O:7][CH2:6]2)[CH2:15][O:3][CH2:4][C:5]2([CH3:9])[CH2:8][O:7][CH2:6]2)[CH2:8][O:7][CH2:6]1

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 76701Propane, 1,3-dibromo-2,2-bis(bromomethyl)-HCID 1378373-Methyl-3-oxetanemethanolHCID 178418361HCID 178418361, compound

Product 1

HCID 57293851Tetrakis-[(3-methyl-3-oxetanyl)methoxymethyl]methaneYield 21.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
100 °C

Procedure

Sodium hydride (50% dispersion in mineral oil, 16.10 g. 0.33 mol) was washed twice with hexanes and was suspended in 500 mL of DMF. Then, 3-hydroxymethyl-3-methyloxetane (34.2 g, 0.33 mol) was added dropwise over 45 min while hydrogen gas was evolved and a beige solid precipitated. The mixture was stirred for 30 min and a solution of tetrakis-(bromomethyl)methane (25.0 g, 0.0645 mol) in 250 mL of DMF was added. The mixture was heated to 100° C. for 64 h when 1H NMR analysis of an aliquot showed that the starting halide had been consumed. The mixture was poured into 500 mL of water and extracted with three portions of 200 mL of methylene chloride. The combined organic extracts were washed with 3 portions of 200 mL of water, dried over magnesium sulfate, and evaporated to give an oil. The oil was cooled to -15° C. for 24 h, and the solid that formed was triturated with ether, filtered, and recrystallized from ethanol to give 6.15 g (21.3%) of tetrakis-[(3-methyl-3-oxetanyl)methoxymethyl]methane, mp 108.5°-109.5° C.

Workup

  1. customa beige solid precipitated
  2. customhad been consumed
  3. additionThe mixture was poured into 500 mL of water
  4. extractionextracted with three portions of 200 mL of methylene chloride
  5. washThe combined organic extracts were washed with 3 portions of 200 mL of water
  6. dry with materialdried over magnesium sulfate
  7. customevaporated
  8. customto give an oil
  9. temperatureThe oil was cooled to -15° C. for 24 h
  10. customthe solid that formed
  11. customwas triturated with ether
  12. filtrationfiltered
  13. customrecrystallized from ethanol

Sources & evidence

ORD record
ord-453d3aef276040608c72772cc9ec2c63
Source dataset
uspto-grants-1997_09
Patent number
US05663289

Reaction notes

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