Dimethylformamide → 3-(Tetradecyloxy)-1,2-propanediol

HRID 375242Notes

Reaction equation

HRID 375242 reaction equation
C[C:2]1([CH3:9])[O:6][CH:5]([CH2:7][OH:8])[CH2:4][O:3]1.Br[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22]CC.CN(C=O)C.[H-].[Na+]>CO>[CH2:2]([O:3][CH2:4][CH:5]([CH2:7][OH:8])[OH:6])[CH2:9][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH3:11]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 7528SolketalHCID 8208Myristyl bromideHCID 24758Sodium hydride

Product 1

HCID 646743-(Tetradecyloxy)-1,2-propanediolYield 4%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a mixture of Solketal (66.1 g, 0.5 mol), 1-bromotetradecane (159.4 g, 0.575 mol), and DMF (800 ml) was added 60% NaH (26.0 g, 0.65 mol) in oil dispersion in 3 portions for 1 hr. The mixture was stirred at room temperature for 1 day and methanol (20 ml) was added to destroy the excess NaH. This was then poured into 1500 ml of ice-water and the aqueous layer was extracted with hexanes (2000 ml). The combined organic layers were evaporated to dryness and the oily residue was refluxed in 10% HCl/methanol (conc. HCl, 250 ml and methanol, 675 ml) for 30 min followed by stirring at room temperature overnight. The white flaky solid was filtered and washed with methanol (122 g). The additional product was obtained from the filtrate (5.7 g); Total 127.7 g (88.5%). The crude product was recrystallized from diethyl ether; Yield 99.7 g (69.1%), mp 57°-58° C.

Workup

  1. customto destroy the excess NaH
  2. additionThis was then poured into 1500 ml of ice-water
  3. extractionthe aqueous layer was extracted with hexanes (2000 ml)
  4. customThe combined organic layers were evaporated to dryness
  5. temperaturethe oily residue was refluxed in 10% HCl/methanol (conc. HCl, 250 ml and methanol, 675 ml) for 30 min
  6. stirringby stirring at room temperature overnight
  7. filtrationThe white flaky solid was filtered
  8. washwashed with methanol (122 g)

Sources & evidence

ORD record
ord-c5d19bf1a64a48dca797660e1d22a0c1
Source dataset
uspto-grants-1996_01
Patent number
US05484911

Reaction notes

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