Ethanol → 2,2-Bis(6-hydroxy-5,5-dimethylhexyl)malonic acid diethyl ester

HRID 1159701Notes

Reaction equation

HRID 1159701 reaction equation
[CH2:1]([O:3][C:4](=[O:41])[C:5]([CH2:26][CH2:27][CH2:28][CH2:29][C:30]([CH3:40])([CH3:39])[CH2:31][O:32]C1CCCCO1)([CH2:11][CH2:12][CH2:13][CH2:14][C:15]([CH3:25])([CH3:24])[CH2:16][O:17]C1CCCCO1)[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:2].C(O)C>Cl.O>[CH2:9]([O:8][C:6](=[O:7])[C:5]([CH2:26][CH2:27][CH2:28][CH2:29][C:30]([CH3:39])([CH3:40])[CH2:31][OH:32])([CH2:11][CH2:12][CH2:13][CH2:14][C:15]([CH3:24])([CH3:25])[CH2:16][OH:17])[C:4]([O:3][CH2:1][CH3:2])=[O:41])[CH3:10]

Participants

5

Reactant 2

HCID 702EthanolHCID 117069512,2-Bis[5,5-dimethyl-6-(tetrahydropyran-2-yloxy)-hexyl]malonic acid diethyl ester

Product 1

HCID 117043932,2-Bis(6-hydroxy-5,5-dimethylhexyl)malonic acid diethyl esterYield 84%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×

Procedure

A solution of 2,2-bis[5,5-dimethyl-6-(tetrahydropyran-2-yloxy)-hexyl]malonic acid diethyl ester (2.92 g, 5.0 mmol) in concentrated hydrochloric acid (2.4 mL) and water (1.6 mL) was heated at reflux for 1 h. Ethanol (8.2 mL) was added and the reaction mixture was heated at reflux for 3 h. The reaction mixture was diluted with water (20 mL) and extracted with diethyl ether (3×20 mL). The combined organic layers were washed with water (20 mL) and brine (20 mL), dried over sodium sulfate, and concentrated in vacuo to afford 2,2-bis(6-hydroxy-5,5-dimethylhexyl)malonic acid diethyl ester (1.74 g, 84%) as an oil. 1H NMR (300 MHz, CDCl3/TMS): δ (ppm): 4.13 (q, 4 H, J=7.2 Hz), 3.25 (s, 4 H), 2.42 (s, 2 H), 1.90-1.75 (m, 4 H), 1.30-1.12 (m, 18 H), 0.84 (s, 12 H). 13C NMR (75 MHz, CDCl3/TMS): δ (ppm): 172.0, 71.7, 60.9, 57.4, 38.2, 34.9, 32.1, 24.8, 24.0, 23.7, 14.0. HRMS (LSIMS, gly): Calcd. for C23H45O6 (MH+): 417.3216, found: 417.3210.

Workup

  1. temperatureat reflux for 1 h
  2. temperaturethe reaction mixture was heated
  3. temperatureat reflux for 3 h
  4. extractionextracted with diethyl ether (3×20 mL)
  5. washThe combined organic layers were washed with water (20 mL) and brine (20 mL)
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-68272691098b40a389648fa1b764199f
Source dataset
uspto-grants-2010_10
Patent number
US07812199B2

Reaction notes

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