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

HRID 1505845Notes

Reaction equation

HRID 1505845 reaction equation
[CH3:1][Si:2]([CH3:25])([CH3:24])[CH2:3][CH2:4][O:5][CH2:6][N:7]1[C:11]2[CH:12]=[N+:13]([O-:18])[C:14]([C:16]#[N:17])=[CH:15][C:10]=2[C:9]2=[CH:19][CH:20]=[CH:21][N+:22]([O-])=[C:8]12.CS([Cl:30])(=O)=O>CN(C)C=O.C(OCC)(=O)C.O>[Cl:30][C:19]1[C:9]2[C:10]3[CH:15]=[C:14]([C:16]#[N:17])[N+:13]([O-:18])=[CH:12][C:11]=3[N:7]([CH2:6][O:5][CH2:4][CH2:3][Si:2]([CH3:25])([CH3:24])[CH3:1])[C:8]=2[N:22]=[CH:21][CH:20]=1.[Cl:30][C:21]1[CH:20]=[CH:19][C:9]2[C:10]3[CH:15]=[C:14]([C:16]#[N:17])[N+:13]([O-:18])=[CH:12][C:11]=3[N:7]([CH2:6][O:5][CH2:4][CH2:3][Si:2]([CH3:25])([CH3:24])[CH3:1])[C:8]=2[N:22]=1

Participants

7

Reactant 2

HCID 31297Methanesulfonyl chlorideHCID 866534929-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile-1,7-dioxide

Product 2

HCID 670274914-Chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile-7-oxideHCID 866534912-chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile-7-oxide

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 9-(2-trimethylsilanylethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile-1,7-dioxide (2.1 g, 5.9 mmol) in N,N-dimethylformamide (50 mL) was treated with methanesulfonyl chloride (0.78 mL, 10.0 mmol), and the reaction mixture was stirred at room temperature for 7 h. 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 6.5:1 mixture with 2-chloro-9-(2-trimethylsilanylethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile-7-oxide respectively as an off-white solid (1.7 g, 77%). The mixture was used in the next step without any further purification. 1H NMR (CDCl3, 400 MHz): 8.86 (s, 1H), 8.39 (d, J=6.4 Hz, 1H), 8.27 (s, 1H), 7.94 (d, J=8.1 Hz, 1H), 7.32 (dd, J=7.9 Hz, 6.5 Hz, 1H), 6.55 (s, 2H), 3.73 (t, J=8.0 Hz, 2H), 0.93 (t, J=8.0 Hz, 2H), −0.04 (s, 9H).

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-2de005358c6e4be58989997adb88394f
Source dataset
uspto-grants-2015_12
Patent number
US09216980B2

Reaction notes

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