Methyl chloroformate → HCID 23147119, compound

HRID 495285Notes

Reaction equation

HRID 495285 reaction equation
[C:1]([C:4]1[C:9]([OH:10])=[CH:8][C:7]([OH:11])=[C:6]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:5]=1[CH2:18][C:19]([O:21][CH3:22])=[O:20])(=O)[CH3:2].C(N(CC)CC)C.[C:30](Cl)(=[O:33])[O:31][CH3:32].[BH4-].[Na+]>O1CCCC1.O>[CH2:1]([C:4]1[C:5]([CH2:18][C:19]([O:21][CH3:22])=[O:20])=[C:6]([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:7]([OH:11])=[CH:8][C:9]=1[O:10][C:30]([O:31][CH3:32])=[O:33])[CH3:2]

Participants

7

Reactant 4

HCID 6586Methyl chloroformateHCID 8471TriethylamineHCID 4311764Sodium borohydrideHCID 86613498HCID 86613498, compound

Product 1

HCID 23147119HCID 23147119, compoundYield 64%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
4 °C

Procedure

Compound 69 (0.12 g, 0.41 mmol) obtained in Example 69 was dissolved in tetrahydrofuran (10 mL), triethylamine (0.15 mL, 1.1 mmol) was added thereto, and the solution was cooled to 4° C. Then, methyl chlorocarbonate (0.081 mL, 1.1 mmol) was added thereto, and the mixture was stirred for 2 hours with heating up to room temperature. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The resulting methyl 2-acetyl-3,5-bis(methoxycarbonyloxy)-6-phenylphenylacetate was dissolved in a mixed solvent of tetrahydrofuran (5.0 mL) and water (5.0 mL), then the solution was cooled to 4° C., and sodium borohydride (73 mg, 1.9 mmol) was added thereto, taking 5 minutes, and then stirred for 1 hour. Water (10 mL) was added to the reaction mixture, and stirred for 10 minutes, and then extracted twice with ethyl acetate (0.10 L). The organic layer was washed with aqueous saturated sodium chloride solution, then dried over anhydrous sodium sulfate, and the solvent was evaporated away under reduced pressure. The resulting residue was purified through preparative thin-layer chromatography (ethyl acetate/n-hexane=1/2) to obtain methyl 6-ethyl-3-hydroxy-5-(methoxycarbonyloxy)-2-phenylphenylacetate (89 mg, 64%).

Workup

  1. temperaturewith heating up to room temperature
  2. filtrationThe reaction mixture was filtered
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. dissolutionThe resulting methyl 2-acetyl-3,5-bis(methoxycarbonyloxy)-6-phenylphenylacetate was dissolved in a mixed solvent of tetrahydrofuran (5.0 mL) and water (5.0 mL)
  5. temperaturethe solution was cooled to 4° C.
  6. waittaking 5 minutes
  7. stirringstirred for 1 hour
  8. stirringstirred for 10 minutes
  9. extractionextracted twice with ethyl acetate (0.10 L)
  10. washThe organic layer was washed with aqueous saturated sodium chloride solution
  11. dry with materialdried over anhydrous sodium sulfate
  12. customthe solvent was evaporated away under reduced pressure
  13. customThe resulting residue was purified through preparative thin-layer chromatography (ethyl acetate/n-hexane=1/2)

Sources & evidence

ORD record
ord-02d5dc3ef93c4999aa3babaeeef9bfbc
Source dataset
uspto-grants-2009_05
Patent number
US07538241B2

Reaction notes

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