Potassium Iodide → 3,4-Bis-octadec-9-enyloxy-benzaldehyde

HRID 604758Notes

Reaction equation

HRID 604758 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].[C:20](=[O:23])([O-])[O-].[K+].[K+].[I-].[K+].[CH3:28][OH:29].C(Cl)(Cl)Cl.[C:34]1(=[O:40])[CH2:39][CH2:38][CH2:37][CH2:36][CH2:35]1>[Al]>[CH2:1]([O:40][C:34]1[CH:39]=[C:38]([CH:37]=[CH:36][C:35]=1[O:23][CH2:20][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH:8]=[CH:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH:28]=[O:29])[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

7

Reactant 5

HCID 4875Potassium IodideHCID 7967CyclohexanoneHCID 11430Potassium CarbonateHCID 58403839-Octadecene, 1-bromo-, (9Z)-2×HCID 21584188Chloroform methanol

Product 1

HCID 862608213,4-Bis-octadec-9-enyloxy-benzaldehydeYield 69%

Reagents, catalysts & solvents 1

HCID 5359268AluminumSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of oleyl bromide (1.8 g, 5.4 mmol) in cyclohexanone (20 ml) was added protocatachualdehyde (0.341 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. TLC (10% MeOH/CHCl3) showed the reaction was complete. The hot reaction mixture was filtered to remove some of the particulates and the solvent was removed in vacuo. The residue was dissolved in CHCl3 (100 mL) and washed with water (2×75 mL). The CHCl3 layer was dried over anhydrous sodium sulphate, filtered and the solvent removed in vacuo to give a dark yellow oil. The oily residue was purified by flash column chromatography (5% EtAc/hexane) to yield the product 8a as a white solid (1.08 g, 69%), Rf=0.3 (5% EtAc/hexane). 1H NMR (CDCl3) d 9.80 (s, 1H, CHO), 7.37 (m, 2H, phenyl), 6.93 (d, 1H, phenyl), 5.33 (t, 4H, olefinic), 4.06 (t, 2H, OCH2), 4.04 (t, 2H, OCH2), 2.01 (m, 8H, CH2C═C), 1.85 (m, 4H, CH2CH2O), 1.50-1.18 (m, 44H, 22×CH2), 0.88 (t, 6H, CH3); 13C NMR (CDCl3) d 191.00, 155.34, 149.95, 130.14, 130.12, 129.97, 126.79, 111.89, 111.04, 69.36, 32.29, 30.16, 29.92, 29.90, 29.88, 29.72, 29.64, 29.62, 29.44, 29.36, 27.60, 26.37, 26.34, 23.09, 14.53; HRMS (FAB): theory for C43H75O3 (M+1), 639.5716; found (M+1), 639.5755. Anal. (C43H74O3): C, H.

Workup

  1. filtrationThe hot reaction mixture was filtered
  2. customto remove some of the particulates
  3. customthe solvent was removed in vacuo
  4. dissolutionThe residue was dissolved in CHCl3 (100 mL)
  5. washwashed with water (2×75 mL)
  6. dry with materialThe CHCl3 layer was dried over anhydrous sodium sulphate
  7. filtrationfiltered
  8. customthe solvent removed in vacuo
  9. customto give a dark yellow oil
  10. customThe oily residue was purified by flash column chromatography (5% EtAc/hexane)

Sources & evidence

ORD record
ord-a3f5a0396a1c4aaa85087dc35ae4ddfb
Source dataset
uspto-grants-2011_03
Patent number
US07910363B1

Reaction notes

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