Potassium Carbonate → HCID 59815574, compound

HRID 2117249Notes

Reaction equation

HRID 2117249 reaction equation
C1(S([CH2:10][C:11]2[CH:16]=[CH:15][C:14]([N+]([O-])=O)=[CH:13][C:12]=2[CH:20]2[O:24][CH2:23][CH2:22][O:21]2)(=O)=O)C=CC=CC=1.[N+:25]([C:28]1[CH:29]=[CH:30]C(CS(C2C=CC=CC=2)(=O)=O)=C([CH:35]=1)C=O)([O-:27])=[O:26].C(/C(/C([O-])=O)=[C:49](\CC)/[C:50]([O-])=[O:51])C.C([O-])([O-])=[O:59].[K+].[K+]>CC(O)=O.O.C(#N)C.C1OCCOCCOCCOCCOCCOC1>[N+:25]([C:28]1[CH:35]=[C:15]2[C:14](=[CH:30][CH:29]=1)[CH:13]=[C:12]([C:20]([O:21][CH2:22][CH3:23])=[O:24])[C:11]([C:10]([O:51][CH2:50][CH3:49])=[O:59])=[CH:16]2)([O-:27])=[O:26]

Participants

9

Reactant 4

HCID 11430Potassium CarbonateHCID 108920885-nitro-2-phenylsulfonylmethylbenzaldehydeHCID 132569602-{2-[(Benzenesulfonyl)methyl]-5-nitrophenyl}-1,3-dioxolaneHCID 22486026HCID 22486026, compound

Product 1

HCID 59815574HCID 59815574, compoundYield 72.8%

Reagents, catalysts & solvents 4

HCID 2855718-Crown-6CatalystHCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

2-(2-Phenylsulfonylmethyl-5-nitrophenyl)-1,3-dioxolane (400 mg, 1.14 mmol) was dissolved in AcOH (8 mL) and water (2 mL). The solution was refluxed for 5 h and then concentrated under reduced pressure. The resulting solid was confirmed as the desired product by NMR and used in the next step without further purification. In a 25 mL round bottom flask, 5-nitro-2-phenylsufonylmethylbenzaldehyde (300 mg, 1.00 mmol), diethylmaleate (195 μL, 207 mg, 1.20 mmol) and 18-crown-6 (13 mg, 0.05 mmol) were dissolved in acetonitrile (10 mL). K2CO3 (700 mg) was added and the resulting mixture was stirred for 30 min. The reaction was refluxed for 3 h, then filtered over celite and concentrated under reduced pressure. The resulting dark oily residue was purified by flash chromatography (30% EtOAc/hexanes) to give diethyl 6-nitro-2,3-naphthalenedicarboxylate (231 mg, 64%, Rf=0.35 20% EtOAc/hexanes). 1H-NMR (400 MHz, CDCl3, δ): 1.42 (t, 3H, J=7.1 Hz), 1.43 (t, 3H, J=7.1 Hz), 4.45 (c, 4H, J=7.1 Hz), 8.07 (d, 1H, J=9.0 Hz), 8.31 (s, 1H), 8.37 (dd, 1H, J1=9.0 Hz, J2=2.1 Hz), 8.47 (s, 1H), 8.87 (d, 1H, J=1.8 Hz). 13C-NMR (100 MHz, CDCl3, δ): 167.1, 166.7, 147.2, 135.9, 132.8, 132.3, 131.9, 130.9, 130.5, 129.9, 129.7, 125.13, 121.9, 62.36, 14.33. HRMS-ESI (m/z): [M+H+] calcd for C16H15NO6 318.0972, found, 318.0986.

Workup

  1. temperatureThe solution was refluxed for 5 h
  2. concentrationconcentrated under reduced pressure
  3. customused in the next step without further purification
  4. temperatureThe reaction was refluxed for 3 h
  5. filtrationfiltered over celite and
  6. concentrationconcentrated under reduced pressure
  7. customThe resulting dark oily residue was purified by flash chromatography (30% EtOAc/hexanes)

Sources & evidence

ORD record
ord-0beebc6961f644a6be10d5af7bc06875
Source dataset
uspto-grants-2008_10
Patent number
US07442529B2

Reaction notes

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