Water → 2,2-Bis[5,5-dimethyl-6-(tetrahydropyran-2-yloxy)-hexyl]malonic acid diethyl ester

HRID 239050Notes

Reaction equation

HRID 239050 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][C:6]([CH3:16])([CH3:15])[CH2:7][O:8][CH:9]1[CH2:14][CH2:13][CH2:12][CH2:11][O:10]1.[C:17]([O:25][CH2:26][CH3:27])(=[O:24])[CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20].[H-].[Na+].[OH2:30]>CS(C)=O.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH2:26]([O:25][C:17](=[O:24])[C:18]([CH2:2][CH2:3][CH2:4][CH2:5][C:6]([CH3:15])([CH3:16])[CH2:7][O:30][CH:11]1[CH2:12][CH2:13][CH2:14][CH2:9][O:10]1)([CH2:2][CH2:3][CH2:4][CH2:5][C:6]([CH3:16])([CH3:15])[CH2:7][O:8][CH:9]1[CH2:14][CH2:13][CH2:12][CH2:11][O:10]1)[C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH3:27]

Participants

7

Reactant 4

HCID 962WaterHCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 103796142-(6-Bromo-2,2-dimethylhexyloxy)-tetrahydropyran

Product 1

HCID 117069512,2-Bis[5,5-dimethyl-6-(tetrahydropyran-2-yloxy)-hexyl]malonic acid diethyl esterYield 82.3%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

Under nitrogen atmosphere, to a solution of 2-(6-bromo-2,2-dimethyl-hexyloxy)-tetrahydropyran (17.6 g, 60 mmol) and diethyl malonate (4.8 g, 30 mmol) in anhydrous DMSO (145 mL) was added sodium hydride (60% dispersion in mineral oil, 2.88 g, 72 mmol) under cooling with a water-bath. Tetra-n-butylammonium iodide (2.1 g, 3.6 mmol) was then added. The mixture was stirred for 16 h at room temperature. Water (140 mL) was added carefully to the reaction mixture under cooling with water-bath. The product was extracted with diethyl ether (3 60 mL) and the combined organic layers were washed with water (4 50 mL) and brine (50 mL). The solution was dried over sodium sulfate and concentrated in vacuo to give 2,2-bis-[5,5-dimethyl-6-(tetrahydropyran-2-yloxy)-hexyl]-malonic acid diethyl ester (17.3 g, 82.3%) as an oil. 1H NMR (300 MHz, CDCl3/TMS): (ppm) 4.41 (t, J=3.1 Hz, 2H), 4.01 (q, J=7.0 Hz, 4H), 3.82-3.70 (m, 2 H), 3.50-3.30 (m, 4 H), 2.87 (d, J=9.1 Hz, 2 H), 1.80-1.35 (m, 16 H), 1.30-0.95 (m, 18 H), 0.88-0.74 (m, 12 H). 13C NMR (75 MHz, CDCl3/TMS): (ppm) 172.0, 99.1, 76.6, 61.9, 60.9, 57.6, 39.2, 34.3, 32.3, 30.7, 25.7, 25.0, 24.6, 24.6, 24.3, 19.5, 14.2.

Workup

  1. temperatureunder cooling with a water-bath
  2. temperatureunder cooling with water-bath
  3. extractionThe product was extracted with diethyl ether (3 60 mL)
  4. washthe combined organic layers were washed with water (4 50 mL) and brine (50 mL)
  5. dry with materialThe solution was dried over sodium sulfate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-731d0980940b424495431af3c26dc6a2
Source dataset
uspto-grants-2014_02
Patent number
US08642653B2

Reaction notes

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