Ethyl bromoacetate → 2,5,8,11,14,17,20,23,26,29-Decaoxahentriacontan-31-oic acid

HRID 1351035Notes

Reaction equation

HRID 1351035 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][O:5][CH2:6][CH2:7][O:8][CH2:9][CH2:10][O:11][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][O:20][CH2:21][CH2:22][O:23][CH2:24][CH2:25][O:26][CH2:27][CH2:28][OH:29].[H-].[Na+].BrC[C:34]([O:36]CC)=[O:35].[OH-].[Na+].O1CCC[CH2:42]1>C(O)C>[CH3:42][O:29][CH2:28][CH2:27][O:26][CH2:25][CH2:24][O:23][CH2:22][CH2:21][O:20][CH2:19][CH2:18][O:17][CH2:16][CH2:15][O:14][CH2:13][CH2:12][O:11][CH2:10][CH2:9][O:8][CH2:7][CH2:6][O:5][CH2:4][CH2:3][O:2][CH2:1][C:34]([OH:36])=[O:35]

Participants

7

Reactant 5

HCID 7748Ethyl bromoacetateHCID 8028TetrahydrofuranHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 11339376Nonaethylene Glycol Monomethyl Ether

Product 1

HCID 101170502,5,8,11,14,17,20,23,26,29-Decaoxahentriacontan-31-oic acid

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of the product of step (d) (20 g) in dry tetrahydrofuran (500 mL) at 0° C. was added sodium hydride (60% dispersion in mineral oil, 2.43 g) portionwise. The reaction was stirred at 0° C. for 30 minutes then ethyl bromoacetate (8.19 g) was added dropwise and the reaction was allowed to warm to 20° C. and stirred for a further 3 hours. Ethanol (100 mL) was then added and stirring was continued at 20° C. for 30 minutes. Sodium hydroxide solution (2M, 100 mL) was then added and the resulting mixture was stirred at 20° C. for 2 hours. The reaction mixture was then partitioned between dichloromethane (700 mL) and water (700 mL). The aqueous layer was acidified to pH 1 by the addition of hydrochloric acid (2M) and then extracted with dichloromethane (3×500 mL). The combined organic layers were dried and the solvent removed in vacuo. Purification by chromatography on silica gel (Biotage), eluting with 10% methanol/1% ammonia (specific gravity 0.880) in dichloromethane gave the title compound as a pale yellow oil (15 g). LC retention time 2.18 mins. Mass spectrum m/z 485 [M+]

Workup

  1. temperatureto warm to 20° C.
  2. stirringstirred for a further 3 hours
  3. stirringstirring
  4. waitwas continued at 20° C. for 30 minutes
  5. stirringthe resulting mixture was stirred at 20° C. for 2 hours
  6. customThe reaction mixture was then partitioned between dichloromethane (700 mL) and water (700 mL)
  7. additionThe aqueous layer was acidified to pH 1 by the addition of hydrochloric acid (2M)
  8. extractionextracted with dichloromethane (3×500 mL)
  9. customThe combined organic layers were dried
  10. customthe solvent removed in vacuo
  11. customPurification by chromatography on silica gel (Biotage)
  12. washeluting with 10% methanol/1% ammonia (specific gravity 0.880) in dichloromethane

Sources & evidence

ORD record
ord-4caba50fe9784cbca7ed14b9a6e412bb
Source dataset
uspto-grants-2007_05
Patent number
US07217409B2

Reaction notes

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