Calcium Carbonate → HCID 86694928, compound

HRID 2204692Notes

Reaction equation

HRID 2204692 reaction equation
[C:1]([O:4][C:5]1[CH:14]=[C:13](C(Br)Br)[C:12]([Br:18])=[CH:11][C:6]=1C(OC)=O)(=O)[CH3:2].[C:19](=[O:22])([O-])[O-:20].[Ca+2].[C:24](=[O:27])([O-])[O-].[K+].[K+].[F:30][C:31]1[CH:38]=[CH:37][C:34]([CH2:35]Br)=[CH:33][CH:32]=1>O1CCOCC1.O.C(OCC)(=O)C>[Br:18][C:12]1[C:13]([CH:24]=[O:27])=[CH:14][C:5]([O:4][CH2:1][C:2]2[CH:37]=[CH:38][C:31]([F:30])=[CH:32][CH:33]=2)=[C:6]([CH:11]=1)[C:19]([O:20][CH2:35][C:34]1[CH:37]=[CH:38][C:31]([F:30])=[CH:32][CH:33]=1)=[O:22]

Participants

8

Reactant 4

HCID 10112Calcium CarbonateHCID 11430Potassium Carbonate2×HCID 680214-Fluorobenzyl bromide2×HCID 66611740HCID 66611740, compound

Product 1

HCID 86694928HCID 86694928, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

To a suspension of methyl 2-(acetyloxy)-5-bromo-4-(dibromomethyl)benzoate (may be prepared as described in Description 23; 1 g, 2.25 mmol) in 1,4-dioxane (5 ml)/water (5 ml) was added calcium carbonate (0.68 g, 6.74 mmol). The mixture was heated in a microwave for 3.5 hours, cooled and the solvent removed in vacuo. The intermediate was suspended in N,N-dimethylformamide (10 ml) and potassium carbonate (0.78 g, 5.62 mmol) and 4-fluorobenzyl bromide (0.61 ml, 4.94 mmol) were added and the mixture stirred for overnight. The solvent was removed in vacuo and the residue taken up in ethyl acetate/H2O (10 ml/10 ml). The organic layer was dried and the solvent removed in vacuo. The residue was redissolved in N,N-dimethylformamide (3 ml) and potassium carbonate (0.78 g, 5.62 mmol) and 4-fluorobenzyl bromide (0.61 ml, 4.94 mmol) added and stirred for 2 hours. Ethyl acetate (20 ml) and water (10 ml) were added, The organic layer was washed further with water (2×10 ml), dried (MgSO4) and the solvent removed in vacuo. Purification by column chromatography (SiO2, 6:1 cyclohexane/ethyl acetate) yielded the title compound as an oil. 920 mg.

Workup

  1. temperatureThe mixture was heated in a microwave for 3.5 hours
  2. temperaturecooled
  3. customthe solvent removed in vacuo
  4. customThe solvent was removed in vacuo
  5. customThe organic layer was dried
  6. customthe solvent removed in vacuo
  7. dissolutionThe residue was redissolved in N,N-dimethylformamide (3 ml)
  8. stirringstirred for 2 hours
  9. washThe organic layer was washed further with water (2×10 ml)
  10. dry with materialdried (MgSO4)
  11. customthe solvent removed in vacuo
  12. customPurification by column chromatography (SiO2, 6:1 cyclohexane/ethyl acetate)

Sources & evidence

ORD record
ord-3e6134614f7049629502dfddd4615733
Source dataset
uspto-grants-2016_06
Patent number
US09365551B2

Reaction notes

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