Cesium carbonate → HCID 131725685, compound

HRID 1793965Notes

Reaction equation

HRID 1793965 reaction equation
[N+]([CH:4](NS(C1C=CC=CC=1)(=O)=O)CCOCCC(NS(C1C=CC=CC=1)(=O)=O)[N+]([O-])=O)([O-])=O.C(=O)([O-])[O-].[Cs+].[Cs+].[CH3:40][S:41]([O:44][CH2:45][CH2:46][CH:47]([CH2:55][C:56]1[CH:61]=[CH:60][C:59]([CH2:62][N:63]([S:71]([C:74]2[CH:79]=[CH:78][CH:77]=[CH:76][C:75]=2[N+:80]([O-:82])=[O:81])(=[O:73])=[O:72])[CH2:64][C:65]2[CH:70]=[CH:69][CH:68]=[CH:67][N:66]=2)=[CH:58][CH:57]=1)[CH2:48][CH2:49][O:50][S:51]([CH3:54])(=[O:53])=[O:52])(=[O:43])=[O:42]>CN(C=O)C.C(OCC)(=O)C>[CH3:54][S:51]([O:50][C:49]1[CH:48]=[C:47]([CH2:55][C:56]2[CH:61]=[CH:60][C:59]([CH2:62][N:63]([S:71]([C:74]3[CH:79]=[CH:78][CH:77]=[CH:76][C:75]=3[N+:80]([O-:82])=[O:81])(=[O:73])=[O:72])[CH2:64][C:65]3[CH:70]=[CH:69][CH:68]=[CH:67][N:66]=3)=[CH:58][CH:57]=2)[CH:46]=[C:45]([O:44][S:41]([CH3:40])(=[O:42])=[O:43])[CH:4]=1)(=[O:53])=[O:52]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 46180391HCID 46180391, compoundHCID 87612330HCID 87612330, compound

Product 1

HCID 131725685HCID 131725685, compoundYield 80.7%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of bis(3-nitrobenzenesulfonylaminopropyl)ether (190 mg, 0.38 mmol) and finely ground, freshly oven-dried cesium carbonate (320 mg, 1.14 mmol) in anhydrous DMF (60 mL) was heated to 80° C. Methanesulfonic acid, 5-methanesulfonyloxy-3-(4-{[(2-nitro-benzenesulfonyl)-pyridin-2-ylmethyl-amino]-methyl}-benzyl)-pentyl ester (250 mg, 0.38 mmol) in DMF (20 mL) was then added to the reaction over a 30 hour period via syringe pump. After complete addition, the reaction was stirred another 30 hours. The mixture was then cooled, diluted with 300 mL ethyl acetate and extracted repeatedly with water. The organic phase was then dried and concentrated, and the residue was purified by column chromatography on silica gel using 25% ethyl acetate in dichloromethane as eluant to afford the desired product (203 mg, 51%). 1H NMR (CDCl3) δ 1.47–1.71 (m, 9H), 2.42 (d, 2H, J=6.1 Hz), 3.15–3.32 (m, 12H), 4.53 (s, 2H), 4.55 (s, 2H), 6.94 (d, 2H, J=6.4 Hz), 7.03 (d, 2H, J=6.4 Hz), 7.05 (d, 1H, J=5.8 Hz), 7.52 (m, 4 H), 7.64 (m, 6 H), 7.91 (m, 5H), 8.44 (d, 1H, J=5.4 Hz).

Workup

  1. additionAfter complete addition
  2. temperatureThe mixture was then cooled
  3. extractionextracted repeatedly with water
  4. customThe organic phase was then dried
  5. concentrationconcentrated
  6. customthe residue was purified by column chromatography on silica gel using 25% ethyl acetate in dichloromethane as eluant

Sources & evidence

ORD record
ord-3e665bd0c0614b21a9426bfc5ef6d710
Source dataset
uspto-grants-2006_04
Patent number
US07022717B2

Reaction notes

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