Hexane → HCID 69108109, compound

HRID 749028Notes

Reaction equation

HRID 749028 reaction equation
[H-].[Na+].C[C:4](P(OC)(O)=O)([C:6]([O-:8])=[O:7])C.[C:14]([O:18][C:19]([NH:21][CH:22]([CH2:26][C:27]1[CH:32]=[CH:31][C:30]([O:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=2[CH:40]=O)=[CH:29][CH:28]=1)[C:23]([OH:25])=[O:24])=[O:20])([CH3:17])([CH3:16])[CH3:15].[CH3:42]CCCCC>C1COCC1>[CH3:42][O:8][C:6](=[O:7])[CH:4]=[CH:40][C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][C:34]=1[O:33][C:30]1[CH:31]=[CH:32][C:27]([CH2:26][CH:22]([NH:21][C:19]([O:18][C:14]([CH3:15])([CH3:17])[CH3:16])=[O:20])[C:23]([OH:25])=[O:24])=[CH:28][CH:29]=1

Participants

6

Reactant 4

HCID 8058HexaneHCID 24758Sodium hydrideHCID 53413272TrimethylphosphonoacetateHCID 72551667HCID 72551667, compound

Product 1

HCID 69108109HCID 69108109, compoundYield 98%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
2.5 °C

Procedure

Sodium hydride (60% in mineral oil, 0.57 g, 14.278 mmol) was washed with anhydrous hexane (3×30 mL) under an atmosphere of argon. Dry THF (50 mL) was added and cooled to 0-5° C. A solution of trimethylphosphonoacetate (1.30 mL, 7.139 mmol) in dry THF (8.0 mL) was added dropwise to the above mixture with stirring. After about 5 min, a solution of the aldehyde 58 (2.5 g, 6.486 mmol) in dry THF (20 mL) was added and the reaction mixture was then brought up to room temperature and stirred. After 30 min, the clear reaction mixture was quenched with 10% citric acid (50 mL) and further acidified to pH ˜2.0 with 2.0 M HCl. The THF was evaporated under reduced pressure and the resulting oily material was extracted with EtOAc (2×200 mL). The organic layer was extracted with water (3×200 mL), and brine (1×200 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to yield the unsaturated ester 59 (2.7 g, 98.0%). 1H NMR (400 MHz, DMSO-d6): 12.62 (s, 1H), 7.91 (dd, J=7.6 and 1.6 Hz, 1H) 7.85 (d, J=16.4 Hz, 1H), 7.42 (dt, J=8.4 and 1.2 Hz, 1H), 7.28 (d, J=13.6, 2H), 7.17 (t, 8.0 Hz, 1H), 7.11 (d, J=8.4 Hz, 1H) 6.93 (d, J=2.8 Hz, 2H), 6.84 (d, J=8.4 Hz, 1H), 6.65 (d, J=16.4 Hz, 1H), 4.08 (m, 1H), 3.68 (s, 3H), 3.03 (dd, J=13.6 and 4.4 Hz, 1H), 2.80 (dd, J=13.6 and 10.0 Hz, 1H), 1.32 (s, 9H).

Workup

  1. customwas then brought up to room temperature
  2. stirringstirred
  3. waitAfter 30 min
  4. customthe clear reaction mixture was quenched with 10% citric acid (50 mL)
  5. customThe THF was evaporated under reduced pressure
  6. extractionthe resulting oily material was extracted with EtOAc (2×200 mL)
  7. extractionThe organic layer was extracted with water (3×200 mL), and brine (1×200 mL)
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-5589ba58b16c4a17a72b15aaf13598e2
Source dataset
uspto-grants-2008_07
Patent number
US07399786B2

Reaction notes

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