Oxalyl chloride → HCID 59610677, compound

HRID 79861Notes

Reaction equation

HRID 79861 reaction equation
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]3[CH:15]=[CH:14][C:13]([C:16]([OH:18])=O)=[CH:12][C:7]=3[CH2:8][O:9]2)=[CH:4][CH:3]=1.[C:19](Cl)(=O)C(Cl)=O.C[Si](C=[N+]=[N-])(C)C.[BrH:32].CC(O)=O.C(=O)(O)[O-].[Na+]>C(Cl)Cl.CCOC(C)=O>[Br:32][CH2:19][C:16]([C:13]1[CH:14]=[CH:15][C:6]2[C:5]3[C:10](=[CH:11][C:2]([Br:1])=[CH:3][CH:4]=3)[O:9][CH2:8][C:7]=2[CH:12]=1)=[O:18]

Participants

8

Reactant 5

HCID 65578Oxalyl chlorideHCID 167693TrimethylsilyldiazomethaneHCID 516892Sodium BicarbonateHCID 21893785Acetic Acid Mixture with Hydrobromic AcidHCID 59610343HCID 59610343, compound

Product 1

HCID 59610677HCID 59610677, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
45 °C

Procedure

To 3-Bromo-6H-benzo[c]chromene-8-carboxylic acid (0.5 mmol) was added a solution of oxalyl chloride in DCM (2.0 N, 5 ml, 10 mmol). The mixture was heated at 45° C. for 2 hours and cooled to 25° C. Excess reagents and solvent were removed under reduced pressure and co-evaporated with toluene. To the solution of above residue in DCM (5 ml) at 0° C. trimethylsilyldiazomethane (2.0 N, 0.75 ml, 1.5 mmol) was added dropwise. The mixture was stirred at 25° C. for 12 hours and was concentrated. The residue was dissolved in EtOAc and was cooled to 0° C. To above solution HBr/HOAc (0.28 ml, 1.5 mmol) was added dropwise. The mixture was stirred at 25° C. for 1 hour. Solid sodium bicarbonate was added and the mixture was stirred for 30 minutes. The mixture was diluted with EtOAc, and was washed with water and brine and was dried with Na2SO4. Concentration gave 2-Bromo-1-(3-bromo-6H-benzo[c]chromen-8-yl)-ethanone, which was used for next step without purification.

Workup

  1. temperaturecooled to 25° C
  2. customExcess reagents and solvent were removed under reduced pressure and co-evaporated with toluene
  3. concentrationwas concentrated
  4. dissolutionThe residue was dissolved in EtOAc
  5. temperaturewas cooled to 0° C
  6. stirringThe mixture was stirred at 25° C. for 1 hour
  7. stirringthe mixture was stirred for 30 minutes
  8. washwas washed with water and brine
  9. dry with materialwas dried with Na2SO4
  10. concentrationConcentration

Sources & evidence

ORD record
ord-b00818f114aa46948533e5b775e6d0d4
Source dataset
uspto-grants-2014_09
Patent number
US08841278B2

Reaction notes

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