Benzyl Bromide → HCID 86694931, compound

HRID 2204714Notes

Reaction equation

HRID 2204714 reaction equation
[C:1]([O:4][C:5]1[CH:14]=[C:13](C(Br)Br)[C:12]([Cl: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-].[Cs+].[Cs+].[CH2:30](Br)[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1>O1CCOCC1.O.C(OCC)(=O)C>[Cl:18][C:12]1[C:13]([CH:24]=[O:27])=[CH:14][C:5]([O:4][CH2:1][C:2]2[CH:13]=[CH:14][CH:5]=[CH:6][CH:11]=2)=[C:6]([CH:11]=1)[C:19]([O:20][CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)=[O:22]

Participants

8

Reactant 4

HCID 7498Benzyl Bromide2×HCID 10112Calcium CarbonateHCID 10796Cesium carbonate2×HCID 66612013HCID 66612013, compound

Product 1

HCID 86694931HCID 86694931, compound

Reagents, catalysts & solvents 3

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

Conditions

Temperature
150 °C

Procedure

A mixture of methyl 2-(acetyloxy)-5-chloro-4-(dibromomethyl)benzoate (may be prepared as described in Description 61; 2.1 g, 5.24 mmol) and calcium carbonate (1.05 g, 10.49 mmol) in 1,4-dioxane (5 ml)/water (5 ml) was heated at 150° C. for 6 hours. The solvent was removed in vacuo and the residue was suspended in N,N-dimethylformamide (5 ml). Cesium carbonate (3.76 g, 11.54 mmol) and benzyl bromide (0.94 ml, 7.87 mmol) were added. The mixture was heated at 50° C. for 18 hours. The N,N-dimethylformamide was removed and the residue was partitioned between 2M HCl (20 ml) and ethyl acetate (15 ml). The organic layer was separated and dried (MgSO4) and the solvent removed in vacuo. The residue was redissolved in N,N-dimethylformamide (5 ml) and cesium carbonate (3.76 g, 11.54 mmol) and benzyl bromide (0.94 ml, 7.87 mmol) were added. The mixture was heated for 2 hours at 50° C. and cooled, then ethyl acetate (15 ml) and water (10 ml) were added. The organic layer was washed with water (2×15 ml). The organic layer was dried (MgSO4) and the solvent removed in vacuo. Purification by column chromatography (6:1 cyclohexane/ethyl acetate) gave the title compound as an off white solid. 1.4 g.

Workup

  1. customThe solvent was removed in vacuo
  2. temperatureThe mixture was heated at 50° C. for 18 hours
  3. customThe N,N-dimethylformamide was removed
  4. customthe residue was partitioned between 2M HCl (20 ml) and ethyl acetate (15 ml)
  5. customThe organic layer was separated
  6. dry with materialdried (MgSO4)
  7. customthe solvent removed in vacuo
  8. dissolutionThe residue was redissolved in N,N-dimethylformamide (5 ml)
  9. temperatureThe mixture was heated for 2 hours at 50° C.
  10. temperaturecooled
  11. washThe organic layer was washed with water (2×15 ml)
  12. dry with materialThe organic layer was dried (MgSO4)
  13. customthe solvent removed in vacuo
  14. customPurification by column chromatography (6:1 cyclohexane/ethyl acetate)

Sources & evidence

ORD record
ord-d8f469d68a2142279de65e226728c9ab
Source dataset
uspto-grants-2016_06
Patent number
US09365551B2

Reaction notes

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