Dichloromethane → HCID 86602648, compound

HRID 2100622Notes

Reaction equation

HRID 2100622 reaction equation
[C:1]([O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)(=[O:4])[CH:2]=[CH2:3].C(N([CH2:18][CH3:19])CC)C.ClCCl.[C:23]([O:26][CH2:27][CH3:28])(=[O:25])[CH3:24]>C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH2:6]([O:5][C:1](=[O:4])/[CH:2]=[CH:3]/[C:9]1[CH:8]=[CH:7][CH:6]=[C:18]([CH3:19])[C:24]=1[C:23]([O:26][CH2:27][CH3:28])=[O:25])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 75617Benzyl acrylate

Product 1

HCID 86602648HCID 86602648, compoundYield 33%

Reagents, catalysts & solvents 1

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)Catalyst

Conditions

Temperature
110 °C

Procedure

To a solution of 6-methylsalicyclic acid ethyl ester (10.0 g, 55.56 mmol) in 250 mL of methylene chloride at −40° C. was added triethylamine (9.3 mL, 66.67 mmol). Then trifluoromethanesulfonic anhydride (9.8 mL, 58.33 mL) was added slowly over 20 min and the reaction was allowed to stir while warming to ambient temperature. The reaction mixture was washed with water and brine, dried (MgSO4) and was concentrated in vacuo to afford a trifluoromethanesulfonate as an oil (18.7 g) which was used without purification. The trifluoromethanesulfonate was taken up in 150 mL of DMF and then there was added benzyl acrylate (14.5 g, 82.5 mmol) and triethylamine (15.3 mL, 110 mmol). The reaction mixture was degassed with a stream of argon and then there was added bis(diphenylphosphino)ferrocene]-dichloropalladium (II) complex with dichloromethane (1:1) (450 mg, 0.55 mmol). The reaction mixture was allowed to stir at 110° C. for 3 days. The reaction mixture was allowed to cool and was diluted with ethyl acetate. The organics were washed with 1 N HCl, water and brine, dried (MgSO4) and concentrated. The residue was purified (ISCO, elution with 0-10% EtOAc/hexane) to afford 5.82 g (33%) of the title compound as an oil. LRMS (ESI): 325.1 (M+H)+.

Workup

  1. customwas used without purification
  2. customThe reaction mixture was degassed with a stream of argon
  3. temperatureto cool
  4. washThe organics were washed with 1 N HCl, water and brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customThe residue was purified
  8. wash(ISCO, elution with 0-10% EtOAc/hexane)

Sources & evidence

ORD record
ord-7606e1f7f9214da084af80eed765d34c
Source dataset
uspto-grants-2009_08
Patent number
US07572805B2

Reaction notes

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