Potassium Hydroxide → 7-Hydroxymethyl-2,2,12,12-tetramethyltridecanedioic acid

HRID 455760Notes

Reaction equation

HRID 455760 reaction equation
[OH-].[K+].C([O:5][C:6](=[O:29])[C:7]([CH3:28])([CH3:27])[CH2:8][CH2:9][CH2:10][CH2:11][CH:12]([CH2:25][OH:26])[CH2:13][CH2:14][CH2:15][CH2:16][C:17]([CH3:24])([CH3:23])[C:18]([O:20]CC)=[O:19])C>O.C(O)C>[OH:26][CH2:25][CH:12]([CH2:13][CH2:14][CH2:15][CH2:16][C:17]([CH3:24])([CH3:23])[C:18]([OH:20])=[O:19])[CH2:11][CH2:10][CH2:9][CH2:8][C:7]([CH3:28])([CH3:27])[C:6]([OH:29])=[O:5]

Participants

5

Reactant 2

HCID 14797Potassium HydroxideHCID 59660142HCID 59660142, compound

Product 1

HCID 596601907-Hydroxymethyl-2,2,12,12-tetramethyltridecanedioic acidYield 81%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

To a homogeneous solution of potassium hydroxide (1.18 g, 21 mmol) in water (1.12 mL) and ethanol (3.8 mL) was added 7-hydroxymethyl-2,2,12,12-tetramethyltridecanedioic acid diethyl ester (2.9 g, 7.5 mmol) and the reaction mixture was heated at reflux for 4 h. The mixture was concentrated in vacuo, cooled to room temperature, and the residue was extracted with diethyl ether (2×50 mL). The pH of the aqueous layer was adjusted to 1 by addition of hydrochloric acid. The product was extracted with diethyl ether (3×50 mL). The combined organic layers were dried over sodium sulfate and concentrated in vacuo to afford the crude product which was purified by column chromatography on silica (hexanes:ethyl acetate=60:40) to yield 7-hydroxymethyl-2,2,12,12-tetramethyltridecanedioic acid (2.0 g, 81%) as an oil. 1H NMR (300 MHz, CDCl3/TMS): δ (ppm): 7.64 (br., 3H), 3.50 (d, 2H, J=4.4 Hz), 1.60-1.20 (m, 17H), 1.16 (s, 12H). 13C NMR (75 MHz, CDCl3/TMS): δ (ppm): 184.3, 65.2, 42.1, 40.5, 40.1, 30.6, 27.1, 25.2, 25.0. HRMS (LSIMS, nba): Calcd. for C18H35O5 (MH+): 331.2484. found 331.2484.

Workup

  1. temperaturethe reaction mixture was heated
  2. temperatureat reflux for 4 h
  3. concentrationThe mixture was concentrated in vacuo
  4. extractionthe residue was extracted with diethyl ether (2×50 mL)
  5. additionThe pH of the aqueous layer was adjusted to 1 by addition of hydrochloric acid
  6. extractionThe product was extracted with diethyl ether (3×50 mL)
  7. dry with materialThe combined organic layers were dried over sodium sulfate
  8. concentrationconcentrated in vacuo
  9. customto afford the crude product which
  10. customwas purified by column chromatography on silica (hexanes:ethyl acetate=60:40)

Sources & evidence

ORD record
ord-9c8e1636072842b4948456325603a21f
Source dataset
uspto-grants-2013_07
Patent number
US08497301B2

Reaction notes

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