Sodium Hydroxide → HCID 86665233, compound

HRID 1053538Notes

Reaction equation

HRID 1053538 reaction equation
[CH2:1]([OH:21])[CH2:2][CH2:3][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].[OH-].[Na+].Br[CH:25]([CH2:33][CH3:34])[C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27]>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1>[CH2:1]([O:21][CH:25]([CH2:33][CH3:34])[C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:2][CH2:3][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

6

Reactant 3

HCID 14798Sodium HydroxideHCID 13124118tert-Butyl 2-bromobutanoate2×HCID 59539494HCID 59539494, compound

Product 1

HCID 86665233HCID 86665233, compoundYield 36%

Reagents, catalysts & solvents 2

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 1140TolueneSolvent

Procedure

Tetrabutylammonium chloride (0.55 g, 1.98 mmol) was added to a solution of (5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaen-1-ol, (3.50 g, 12.1 mmol) in toluene (35 mL) at ambient temperature under nitrogen. An aqueous solution of sodium hydroxide (50% (w/w), 11.7 mL) was added under vigorous stirring at room temperature, followed by t-butyl 2-bromobutyrate (5.41 g, 24.3 mmol). The resulting mixture was heated to 50° C. and additional t-butyl 2-bromobutyrate was added after 1.5 hours (2.70 g, 12.1 mmol), 3.5 hours (2.70 g, 12.1 mmol) and 4.5 hours (2.70 g, 12.1 mmol) and stirred for 12 hours in total. After cooling to room temperature, ice water (25 mL) was added and the resulting two phases were separated. The organic phase was washed with a mixture of NaOH (5%) and brine, dried (MgSO4), filtered and concentrated. The residue was purified by flash chromatography on silica gel using increasingly polar mixtures of heptane and ethyl acetate (100:0→95:5) as eluent. Concentration of the appropriate fractions afforded 1.87 g (36% yield) of the title compound as an oil. 1H NMR (300 MHz, CDCl3): δ 0.85-1.10 (m, 6H), 1.35-1.54 (m, 11H), 1.53-1.87 (m, 4H), 1.96-2.26 (m, 4H), 2.70-3.02 (m, 8H), 3.31 (dt, 1H), 3.51-3.67 (m, 2H), 5.10-5.58 (m, 10H).

Workup

  1. temperatureThe resulting mixture was heated to 50° C.
  2. stirringstirred for 12 hours in total
  3. temperatureAfter cooling to room temperature
  4. customthe resulting two phases were separated
  5. washThe organic phase was washed with a mixture of NaOH (5%) and brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by flash chromatography on silica gel using
  10. temperatureincreasingly polar mixtures of heptane and ethyl acetate (100:0→95:5) as eluent

Sources & evidence

ORD record
ord-d93c6351e96a4a5e9430545993343fdc
Source dataset
uspto-grants-2016_07
Patent number
US09394228B2

Reaction notes

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