Diethyl Ether → 1-(1,1-Dimethylethyl)-3-(phenylmethyl)-2-undecylpropanedioate

HRID 1778646Notes

Reaction equation

HRID 1778646 reaction equation
[H-].[Na+].[C:3]([O:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)(=[O:12])[CH2:4][C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6].Br[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32].CCOCC>CN(C=O)C.O>[CH2:32]([CH:4]([C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6])[C:3]([O:13][CH2:14][C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)=[O:12])[CH2:31][CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH3:22]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 127441-BromoundecaneHCID 24758Sodium hydrideHCID 2736712Benzyl tert-butyl malonate

Product 1

HCID 1178370741-(1,1-Dimethylethyl)-3-(phenylmethyl)-2-undecylpropanedioateYield 71%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent3×

Procedure

To a suspension of NaH (160 mg, 4.0 mmol) in DMF (8 mL) at 0° C. under N2, was added benzyl tert-butyl malonate (1.0 g, 4.0 mmol) in DMF (2 mL). The mixture was stirred for 50 min after which 1-bromoundecane in DMF (2 mL) was added. After an additional hour of stirring the reaction was allowed to warm to room temperature. The reaction was maintained overnight. Et2O (100 mL) and water (20 mL) were added to partition the reaction. The aqueous phase was extracted with Et2O (100 mL), and the combined organics dried over Na2SO4. The solvent was evaporated and the residue purified by flash column (C18 12 g, 40-100% ACN/water+0.1% TFA) to yield the title compound as a colorless oil (1.14 g, 2.82 mmol, 71%): LCMS Method F Rt=1.58 min, M+Na 427.4; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.84-0.96 (m, 3H) 1.28 (br. s, 12H) 1.31 (m, J=3.90 Hz, 6H) 1.41 (s, 9H) 1.88 (q, J=7.38 Hz, 2H) 3.29 (t, J=7.58 Hz, 1H) 5.19 (q, J=12.27 Hz, 2H) 7.30-7.42 (m, 5H).

Workup

  1. additionwas added
  2. temperatureThe reaction was maintained overnight
  3. customto partition
  4. customthe reaction
  5. extractionThe aqueous phase was extracted with Et2O (100 mL)
  6. dry with materialthe combined organics dried over Na2SO4
  7. customThe solvent was evaporated
  8. customthe residue purified by flash column (C18 12 g, 40-100% ACN/water+0.1% TFA)

Sources & evidence

ORD record
ord-9772a64e257a4f4f9c61ecc461efe416
Source dataset
uspto-grants-2016_02
Patent number
US09266925B2

Reaction notes

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