Hydrochloric Acid → 3,4-Bis-octadec-9-enyloxy-benzoic acid

HRID 604759Notes

Reaction equation

HRID 604759 reaction equation
[CH2:1](Br)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8]/[CH:9]=[CH:10]\[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18].[OH:20][C:21]1[CH:22]=[C:23]([CH:29]=[CH:30][C:31]=1[OH:32])[C:24]([O:26]CC)=[O:25].C(=O)([O-])[O-].[K+].[K+].[I-].[K+].[OH-].[K+].Cl>C1(=O)CCCCC1.[Al].O>[CH2:1]([O:20][C:21]1[CH:22]=[C:23]([CH:29]=[CH:30][C:31]=1[O:32][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH:9]=[CH:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[C:24]([OH:26])=[O:25])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH:9]=[CH:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18]

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 4875Potassium IodideHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 77547Ethyl 3,4-DihydroxybenzoateHCID 58403839-Octadecene, 1-bromo-, (9Z)-2×

Product 1

HCID 671440483,4-Bis-octadec-9-enyloxy-benzoic acidYield 70%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 7967CyclohexanoneSolventHCID 5359268AluminumSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of oleyl bromide (1.8 g, 5.4 mmol) in cyclohexanone (20 ml) was added ethyl 3,4-dihydroxybenzoate 7b (0.45 g, 2.5 mmol), potassium carbonate (1.02 g, 7.4 mmol) and potassium iodide (0.05 g, 0.3 mmol). The suspension was stirred at 100° C. for 18 hours under nitrogen. Due to the light sensitivity of the oleyl bromide the flask was covered in aluminum foil. The hot reaction mixture was filtered to remove some of the particulates and the solvent was removed in vacuo. The residue containing ester 8b was dissolved in a solution of ethanol (20 mL) containing potassium hydroxide (0.8 g, 20 mmol) and refluxed for 4 h. The hot reaction mixture was added to water (30 mL) and acidifying with 1M HCl to pH 1 resulted in the precipitation of a white solid. The solid 8c was filtered off and washed several times with water. The crude acid was re-crystallized from ethanol (10 mL) to give the product 8c as a white solid (1.14 g, 70%); 1H NMR (500 MHz, CDCl3) d 7.73 (dd, 1H, phenyl), 7.58 (d, 1H, phenyl), 6.89 (d, 1H, phenyl), 5.35 (t, 4H, olefinic), 4.05 (2×t, 4H, 2×OCH2), 2.01 (m, 8H, CH2C═C), 1.85 (m, 4H, CH2CH2O), 1.48 (quin, 4H, 2×CH2), 1.41-1.19 (m, 40H, 20×CH2), 0.88 (t, 6H, CH3).

Workup

  1. filtrationThe hot reaction mixture was filtered
  2. customto remove some of the particulates
  3. customthe solvent was removed in vacuo
  4. additionThe residue containing ester 8b
  5. dissolutionwas dissolved in a solution of ethanol (20 mL)
  6. temperaturerefluxed for 4 h
  7. customresulted in the precipitation of a white solid
  8. filtrationThe solid 8c was filtered off
  9. washwashed several times with water
  10. customThe crude acid was re-crystallized from ethanol (10 mL)

Sources & evidence

ORD record
ord-28117e9fceb74856b82bfcf67a0829d2
Source dataset
uspto-grants-2011_03
Patent number
US07910363B1

Reaction notes

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