Carbon Tetrachloride → Methyl 2-(4-(bis(benzyloxy)phosphoryloxy)phenyl)acetate

HRID 2100369Notes

Reaction equation

HRID 2100369 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=1.C(Cl)(Cl)(Cl)Cl.CCN(C(C)C)C(C)C.[P:27]([O-:44])([O:36][CH2:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)[O:28][CH2:29][C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>C(#N)C.CN(C1C=CN=CC=1)C>[CH2:29]([O:28][P:27]([O:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:8][C:9]([O:11][CH3:12])=[O:10])=[CH:6][CH:7]=1)([O:36][CH2:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)=[O:44])[C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1

Participants

7

Reactant 4

HCID 5943Carbon TetrachlorideHCID 81531DiisopropylethylamineHCID 518900Benzeneacetic acid, 4-hydroxy-, methyl esterHCID 21904359Dibenzylphosphite

Product 1

HCID 57799050Methyl 2-(4-(bis(benzyloxy)phosphoryloxy)phenyl)acetateYield 88.5%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6342AcetonitrileSolvent

Procedure

To a solution of methyl 2-(4-hydroxyphenyl)acetate (1.89 g, 11.4 mmol) in acetonitrile (90 mL) at −10° C. was added CCl4 (5.5 mL, 57 mmol), DIPEA (4.16 mL, 23.9 mmol) and DMAP (139 mg, 1.14 mmol). After stirring for 10 mins, the mixture was added dibenzyl phosphite (3.7 mL, 16.5 mmol) slowly to keep the temperature below −10° C. The reaction was stirred at −10° C. for 1 h. The reaction was quenched with aqueous K2HPO4 (0.5 M) in acetonitrile (60 mL) and allowed to stirred at rt. The mixture was extracted by ethyl acetate (150 mL×3). The combined organic layers was washed with water and brine, dried over Na2SO4, filtered and concentrated under vacuum. The residue was subjected to ISCO (30-50% AcOEt/hexanes) to give the title compound (4.3 g, 88.5% yield) as a colorless oil.

Workup

  1. customthe temperature below −10° C
  2. stirringThe reaction was stirred at −10° C. for 1 h
  3. customThe reaction was quenched with aqueous K2HPO4 (0.5 M) in acetonitrile (60 mL)
  4. stirringto stirred at rt
  5. extractionThe mixture was extracted by ethyl acetate (150 mL×3)
  6. washThe combined organic layers was washed with water and brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-e3e83edaa85f472b85c026b5b15a26ad
Source dataset
uspto-grants-2009_08
Patent number
US07572795B2

Reaction notes

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