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

HRID 60248Notes

Reaction equation

HRID 60248 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-trimethylsilanyl-ethoxymethyl)-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 ambient temperature for 7 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 6.5:1 mixture with 2-chloro-9-(2-trimethylsilanyl-ethoxymethyl)-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 triturated in ethyl acetate (10 mL) overnight and the remaining solid was collected by vacuum filtration and washed with ethyl acetate (5 mL) to afford the title compound with >98% purity. 1H NMR (400 MHz, CDCl3) δ 8.86 (s, 1H), 8.39 (d, J=6.4, 1H), 8.27 (s, 1H), 7.94 (d, J=8.1, 1H), 7.32 (dd, J=7.9, 6.5, 1H), 6.55 (s, 2H), 3.73 (t, J=8.0, 2H), 0.93 (t, J=8.0, 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-d1bc207c6bcc4625851d5e89e175cfab
Source dataset
uspto-grants-2016_09
Patent number
US09440976B2

Reaction notes

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