2-Cyano-4-nitrobenzene-1-sulfonyl chloride → Methyl 7-(2-cyano-4-nitrobenzenesulfonamido)-4-methylcoumarin-3-acetate

HRID 2369749Notes

Reaction equation

HRID 2369749 reaction equation
[NH2:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([CH3:18])=[C:7]([CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1.[C:19]([C:21]1[CH:26]=[C:25]([N+:27]([O-:29])=[O:28])[CH:24]=[CH:23][C:22]=1[S:30](Cl)(=[O:32])=[O:31])#[N:20]>N1C=CC=CC=1.C(Cl)Cl.C(Cl)Cl.CCOC(C)=O>[C:19]([C:21]1[CH:26]=[C:25]([N+:27]([O-:29])=[O:28])[CH:24]=[CH:23][C:22]=1[S:30]([NH:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([CH3:18])=[C:7]([CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1)(=[O:32])=[O:31])#[N:20]

Participants

6

Reactant 2

HCID 433636332-Cyano-4-nitrobenzene-1-sulfonyl chlorideHCID 86668467methyl2-(7-amino-4-methyl-2-oxo-2H-chromen-3-yl)acetate2×

Product 1

HCID 86668468Methyl 7-(2-cyano-4-nitrobenzenesulfonamido)-4-methylcoumarin-3-acetate

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolventHCID 21875418Pyridine methylene chlorideSolvent

Procedure

Methyl 7-amino-4-methylcoumarin-3-acetate (compound 1 in FIG. 2) (34.0 mg, 0.14 mmol) synthesized in Example 1(1) was dissolved in pyridine/CH2Cl2 (1.4 ml, 1:1), 2-cyano-4-nitrobenzenesulfonyl chloride (CNS chloride; 63.8 mg, 0.26 mmol, 1.9 equivalents) dissolved in CH2Cl2 (0.5 ml) was added under cooling on ice, and the mixture was stirred. The next day, the disappearance of the starting materials was confirmed by TLC and the reaction mixture was diluted with EtOAc, and partitioned between saturated aqueous NaHCO3 solution and H2O. The organic layer was washed with saturated brine and dried over Na2SO4. The solvent was evaporated, and the residue was purified by silica gel column chromatography (eluate: 1% acetic acid-containing hexane:EtOAc=1:1) (compound 2a: 32.0 mg, 0.07 mmol, 51%).

Workup

  1. additionwas added
  2. temperatureunder cooling on ice
  3. custompartitioned between saturated aqueous NaHCO3 solution and H2O
  4. washThe organic layer was washed with saturated brine
  5. dry with materialdried over Na2SO4
  6. customThe solvent was evaporated
  7. customthe residue was purified by silica gel column chromatography (eluate: 1% acetic acid-containing hexane:EtOAc=1:1) (compound 2a: 32.0 mg, 0.07 mmol, 51%)

Sources & evidence

ORD record
ord-1bfbf38445dc44ae8301cd0ee3fdeeee
Source dataset
uspto-grants-2014_04
Patent number
US08709721B2

Reaction notes

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