Methanesulfonyl chloride → 6-Bromo-4-chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-7-oxide

HRID 60316

Reaction equation

HRID 60316 reaction equation
[Br:1][C:2]1[N+:10]([O-:11])=[CH:9][C:8]2[N:7]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[C:6]3=[N+:20]([O-])[CH:21]=[CH:22][CH:23]=[C:5]3[C:4]=2[CH:3]=1.CS([Cl:29])(=O)=O>CN(C)C=O.C(OCC)(=O)C.O>[Br:1][C:2]1[N+:10]([O-:11])=[CH:9][C:8]2[N:7]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[C:6]3[N:20]=[CH:21][CH:22]=[C:23]([Cl:29])[C:5]=3[C:4]=2[CH:3]=1.[Br:1][C:2]1[N+:10]([O-:11])=[CH:9][C:8]2[N:7]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[C:6]3[N:20]=[C:21]([Cl:29])[CH:22]=[CH:23][C:5]=3[C:4]=2[CH:3]=1

Participants

7

Reactant 2

HCID 31297Methanesulfonyl chlorideHCID 866560446-Bromo-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-1,7-dioxide

Product 2

HCID 866560456-Bromo-4-chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-7-oxideHCID 866560466-bromo-2-chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-7-oxide

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 6-bromo-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-1,7-dioxide (1 g, 2.4 mmol) in N,N-dimethylformamide (19 mL) was treated with methanesulfonyl chloride (0.38 mL, 4.9 mmol) and the reaction mixture was stirred at ambient temperature for 3 hours. The reaction mixture was then diluted with ethyl acetate (150 mL) and water (200 mL). The layers were separated and the organic layer was dried over sodium sulfate, filtered, concentrated in vacuo, and purified by flash chromatography (silica, 40 g, ISCO, 5-85% ethyl acetate in heptane) to afford the title compound as a 4:1 mixture with 6-bromo-2-chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-7-oxide respectively as an off-white solid (100 mg, 10%). The mixture was used in the next step without any further purification.

Workup

  1. customThe layers were separated
  2. dry with materialthe organic layer was dried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. custompurified by flash chromatography (silica, 40 g, ISCO, 5-85% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-a0a756f94293465f820dd26555d9f59d
Source dataset
uspto-grants-2016_09
Patent number
US09440976B2

Linked notes

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