Pyridine → Methyl 8-(2-bromo-4-fluorobenzenesulfonylamino)-4,5-dihydro-3,6-dioxa-benzo[e]azulene-7-carboxylate

HRID 1778336Notes

Reaction equation

HRID 1778336 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9](Cl)(=[O:11])=[O:10].[NH2:13][C:14]1[CH:27]=[CH:26][C:17]2[C:18]3[CH:19]=[CH:20][O:21][C:22]=3[CH2:23][CH2:24][O:25][C:16]=2[C:15]=1[C:28]([O:30][CH3:31])=[O:29].N1C=CC=CC=1>C(Cl)Cl>[Br:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:13][C:14]1[CH:27]=[CH:26][C:17]2[C:18]3[CH:19]=[CH:20][O:21][C:22]=3[CH2:23][CH2:24][O:25][C:16]=2[C:15]=1[C:28]([O:30][CH3:31])=[O:29])(=[O:11])=[O:10]

Participants

5

Reactant 3

HCID 1049PyridineHCID 27782162-Bromo-4-fluorobenzene-1-sulfonyl chlorideHCID 66685816Methyl 8-amino-4,5-dihydro-3,6-dioxabenzo[e]azulene-7-carboxylate2×

Product 1

HCID 66685629Methyl 8-(2-bromo-4-fluorobenzenesulfonylamino)-4,5-dihydro-3,6-dioxa-benzo[e]azulene-7-carboxylateYield 95.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2-Bromo-4-fluorobenzenesulfonyl chloride (0.55 g) was added to a solution of methyl 8-amino-4,5-dihydro-3,6-dioxabenzo[e]azulene-7-carboxylate (Intermediate 15, 0.47 g) and pyridine (3 mL) in DCM (5 mL) and the mixture was stirred for 18 hours. The mixture was evaporated to dryness and water and ethyl acetate were added. The organic layer was separated, dried (MgSO4) and filtered. The filtrate was evaporated to dryness and the residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 5-25% to give methyl 8-(2-bromo-4-fluorobenzenesulfonylamino)-4,5-dihydro-3,6-dioxa-benzo[e]azulene-7-carboxylate (0.86 g) as a white solid.

Workup

  1. customThe mixture was evaporated to dryness and water and ethyl acetate
  2. additionwere added
  3. customThe organic layer was separated
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. customThe filtrate was evaporated to dryness
  7. customthe residue was purified by chromatography on silica
  8. washeluting with a mixture of ethyl acetate and cyclohexane with a gradient of 5-25%

Sources & evidence

ORD record
ord-a0c415949a6c46829af0b3fb0d0ec6d1
Source dataset
uspto-grants-2016_02
Patent number
US09266896B2

Reaction notes

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