Heptane → HCID 86665238, compound

HRID 1028084Notes

Reaction equation

HRID 1028084 reaction equation
[OH-].[Na+].[CH2:3]([OH:23])[CH2:4][CH2:5][CH2:6]/[CH:7]=[CH:8]\[CH2:9]/[CH:10]=[CH:11]\[CH2:12]/[CH:13]=[CH:14]\[CH2:15]/[CH:16]=[CH:17]\[CH2:18]/[CH:19]=[CH:20]\[CH2:21][CH3:22].[C:24]([O:28][C:29](=[O:34])[CH:30](Br)[CH2:31]C)([CH3:27])([CH3:26])[CH3:25].[CH3:35][CH2:36]CCCCC>S(=O)(=O)(O)[O-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1>[CH2:3]([O:23][CH:30]([CH3:31])[C:29]([O:28][C:24]([CH3:25])([CH3:26])[CH3:27])=[O:34])[CH2:4][CH2:5]/[CH:6]=[CH:7]\[CH2:8]/[CH:9]=[CH:10]\[CH2:11]/[CH:12]=[CH:13]\[CH2:14]/[CH:15]=[CH:16]\[CH2:17]/[CH:18]=[CH:19]\[CH2:20]/[CH:21]=[CH:22]\[CH2:35][CH3:36]

Participants

7

Reactant 4

HCID 8900HeptaneHCID 14798Sodium HydroxideHCID 13124118tert-Butyl 2-bromobutanoate2×HCID 59539494HCID 59539494, compound

Product 1

HCID 86665238HCID 86665238, compound

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
50 °C

Procedure

An aqueous solution of sodium hydroxide (50% (w/w), 6 ml) was added portionwise to a mixture of (5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaen-1-ol (2.01 g, 6.39 mmol), tert-butyl-2-bromobutyrat (2.85 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 22 hrs. Additional tert-butyl-2-bromobutyrat (1.43 g, 6.39 mmol) and (1.44 g, 6.44 mmol) was added after 1½ hrs and 3 hrs respectively. The mixture was cooled and added ice-water (˜50 ml) and heptane (50 ml), the phases were separated and the organic phase was concentrated under reduced pressure. Flash chromatography on silica gel (30 g) eluting with heptane-heptane/EtOAc (99:1) yielded 2.12 g of the title compound as a liquid. 1H NMR (300 MHz, CDCl3) δ 0.94-1.04 (m, 6H), 1.47 (s, 9H), 1.68-1.85 (m, 4H), 1.93-2.20 (m, 4H), 2.80-2.86 (m, 10H), 3.28-3.36 (m, 1H), 3.55-3.63 (m, 2H), 5.27-5.43 (m, 12H)

Workup

  1. stirringThe reaction mixture was stirred at 50° C. for a total of 22 hrs
  2. temperatureThe mixture was cooled
  3. customthe phases were separated
  4. concentrationthe organic phase was concentrated under reduced pressure
  5. washFlash chromatography on silica gel (30 g) eluting with heptane-heptane/EtOAc (99:1)

Sources & evidence

ORD record
ord-b3fcf8b52cd84787bd91e839da111cca
Source dataset
uspto-grants-2014_05
Patent number
US08735436B2

Reaction notes

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