Water → HCID 86665239, compound

HRID 1028086Notes

Reaction equation

HRID 1028086 reaction equation
[OH-].[Na+].[CH2:3]([OH:21])[CH2:4]/[CH:5]=[CH:6]\[CH2:7]/[CH:8]=[CH:9]\[CH2:10]/[CH:11]=[CH:12]\[CH2:13]/[CH:14]=[CH:15]\[CH2:16]/[CH:17]=[CH:18]\[CH2:19][CH3:20].[C:22]([O:26][C:27](=[O:32])[CH:28](Br)[CH2:29][CH3:30])([CH3:25])([CH3:24])[CH3:23].O>S(=O)(=O)(O)[O-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1.CCCCCCC>[CH2:3]([O:21][CH:28]([CH2:29][CH3:30])[C:27]([O:26][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:32])[CH2:4]/[CH:5]=[CH:6]\[CH2:7]/[CH:8]=[CH:9]\[CH2:10]/[CH:11]=[CH:12]\[CH2:13]/[CH:14]=[CH:15]\[CH2:16]/[CH:17]=[CH:18]\[CH2:19][CH3:20]

Participants

8

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 13124118tert-Butyl 2-bromobutanoate2×HCID 86665240HCID 86665240, compound

Product 1

HCID 86665239HCID 86665239, compoundYield 60.4%

Reagents, catalysts & solvents 3

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 1140TolueneSolventHCID 8900HeptaneSolvent

Conditions

Temperature
50 °C

Procedure

An aqueous solution of sodium hydroxide (50% (w/w), 6 mL) was added portionwise to a mixture of (3Z,6Z,9Z,12Z,15Z)-octadeca-3,6,9,12,15-pentaen-1-ol (1.66 g, 6.37 mmol), tert-butyl-2-bromobutyrat (2.86 g, 12.8 mmol) and tetrabutylammonium bisulfate (0.65 g, 1.91 mmol) in toluene (12 ml). The reaction mixture was vigorously stirred under N2-atmosphere and warmed to 50° C. The reaction mixture was stirred at 50° C. for a total of 25 hrs. Additional tert-butyl-2-bromobutyrat (1.43 g, 6.41 mmol) and (1.42 g, 6.38 mmol) was added after 1½ hrs and 3 hrs respectively. The mixture was cooled to room temperature and added water (30 mL) and heptane (50 mL), the resulting two phases were separated and the organic phase was dried (Na2SO4), filtered and evaporated under reduced pressure. Flash chromatography on silica gel (30 g) eluting with heptane-heptane/EtOAc (99:1) yielded 1.55 g of the title compound as a liquid. 1H NMR (300 MHz, CDCl3) δ 0.96 (t, 3H), 0.97 (t, 3H), 1.48 (s, 9H), 1.64-1.86 (m, 2H), 2.03-2.12 (m, 2H), 2.39 (dd, J=12.1, 6.7 Hz, 2H), 2.79-2.86 (m, 8H), 3.29-3.37 (m, 1H), 3.57-3.66 (m, 2H), 5.27-5.49 (m, 10H).

Workup

  1. stirringThe reaction mixture was stirred at 50° C. for a total of 25 hrs
  2. temperatureThe mixture was cooled to room temperature
  3. customthe resulting two phases were separated
  4. dry with materialthe organic phase was dried (Na2SO4)
  5. filtrationfiltered
  6. customevaporated under reduced pressure
  7. washFlash chromatography on silica gel (30 g) eluting with heptane-heptane/EtOAc (99:1)

Sources & evidence

ORD record
ord-dc0563c60dea463bbaf7cdb41592ef5f
Source dataset
uspto-grants-2014_05
Patent number
US08735436B2

Reaction notes

Loading…