1-Bromododecane → Diethyl dodecyl(methyl)propanedioate

HRID 622317Notes

Reaction equation

HRID 622317 reaction equation
[CH3:1][CH:2]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].Br[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]>CCOCC>[CH2:16]([C:2]([CH3:1])([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]

Participants

5

Reactant 3

HCID 89191-BromododecaneHCID 11857Diethyl methylmalonateHCID 24758Sodium hydride

Product 1

HCID 15573740Diethyl dodecyl(methyl)propanedioateYield 88%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 48.72 g (0.277 mol) of diethyl methylmalonate (available from Aldrich Chem. Co., Catalog No. 12,613-6) in 60 ml of N1N-dimethyl formamide (DMF) is added dropwise to a stirred solution of 6.86 g (0.277 mol) of sodium hydride (NaH) in DMF. The reaction mixture is heated during the dropwise addition of a solution of 72.17 g (0.284 mol) of 1-bromododecane (Aldrich Chem. Co., catalog no. B6,555-1) in 60 ml DMF. The reaction is heated to 80° C. and stirred overnight, after which the NaBr that precipitated is filtered and the DMF removed in vacuo. The oily residue obtained is dissolved in ether and filtered again to remove all NaBr. The ether solution is washed with water followed by saturated NaCl. The solution is dried over anhydrous sodium sulfate and the ether is removed under reduced pressure to yield a clear, yellow oil. Fractional distillation (130°-138° C., 0.007 mm Hg) gives 82.28 g (88% overall yield) of diethyl dodecyl-methylmalonate as a clear oil. The oil is dissolved in 175 ml of anhydrous ether, and the solution is added dropwise to a suspension of 19.21 g (0.480 mol) of lithium aluminum hydride. The reaction is stirred overnight, carefully quenched, and filtered. The solvent is removed in vacuo and the solid obtained is recrystallized and dried to give 51.00 g (81% overall yield) of 2-dodecyl-2-methylpropane-1,3-diol as a white solid (mp 67°-68° C.).

Workup

  1. customafter which the NaBr that precipitated
  2. filtrationis filtered
  3. customthe DMF removed in vacuo
  4. customThe oily residue obtained
  5. filtrationfiltered again
  6. customto remove all NaBr
  7. washThe ether solution is washed with water
  8. dry with materialThe solution is dried over anhydrous sodium sulfate
  9. customthe ether is removed under reduced pressure
  10. customto yield a clear, yellow oil
  11. distillationFractional distillation (130°-138° C., 0.007 mm Hg)

Sources & evidence

ORD record
ord-b7043e744d0b474fab8e0a5100ce4da9
Source dataset
uspto-grants-1988_09
Patent number
US04770759

Reaction notes

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