2-Bromo-4-fluorobenzene-1-sulfonyl chloride → methyl 7-(2-bromo-4-fluorobenzenesulfonylamino)-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate

HRID 2200336Notes

Reaction equation

HRID 2200336 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[C:27]([C:28]([O:30][CH3:31])=[O:29])=[C:26]2[C:17]([C:18]3[CH:19]=[CH:20][N:21]=[N:22][C:23]=3[CH2:24][O:25]2)=[CH:16][CH:15]=1>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[C:27]([C:28]([O:30][CH3:31])=[O:29])=[C:26]2[C:17]([C:18]3[CH:19]=[CH:20][N:21]=[N:22][C:23]=3[CH2:24][O:25]2)=[CH:16][CH:15]=1)(=[O:11])=[O:10]

Participants

5

Reactant 2

HCID 27782162-Bromo-4-fluorobenzene-1-sulfonyl chlorideHCID 89705423methyl 7-amino-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate2×

Product 1

HCID 89705396methyl 7-(2-bromo-4-fluorobenzenesulfonylamino)-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylateYield 53.8%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

2-Bromo-4-fluorobenzenesulfonyl chloride (0.631 g) was added to a solution of methyl 7-amino-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate (Intermediate 6, 0.395 g) in pyridine (20 mL) and DCM (20 mL) and the mixture was allowed to stand at room temperature for 4 days. The resulting solution was evaporated in vacuo, and the residue was partitioned between a mixture of DCM and water and filtered through a phase separator. The filtrate was evaporated to dryness, and the residue was azeotroped with toluene. The residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 50-100% to give methyl 7-(2-bromo-4-fluorobenzenesulfonylamino)-10H-9-oxa-1,2-diaza-phenanthrene-8-carboxylate (0.408 g) as an off-white solid.

Workup

  1. customThe resulting solution was evaporated in vacuo
  2. customthe residue was partitioned between a mixture of DCM and water
  3. filtrationfiltered through a phase separator
  4. customThe filtrate was evaporated to dryness
  5. customthe residue was azeotroped with toluene
  6. customThe residue was purified by chromatography on silica
  7. washeluting with a mixture of ethyl acetate and cyclohexane with a gradient of 50-100%

Sources & evidence

ORD record
ord-d0bd37e886934910bb0503b4b67f535e
Source dataset
uspto-grants-2016_06
Patent number
US09359369B2

Reaction notes

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