Acetic Acid → HCID 68194936, compound

HRID 2370642Notes

Reaction equation

HRID 2370642 reaction equation
[N:1]1([C:6]2[CH:27]=[CH:26][C:9]([CH2:10][N:11]3[CH2:20][C:19]([CH3:22])([CH3:21])[C:18]4[C:13](=[CH:14][C:15]([N+:23]([O-])=O)=[CH:16][CH:17]=4)[CH2:12]3)=[CH:8][CH:7]=2)[CH:5]=[CH:4][N:3]=[CH:2]1.C(O)(=O)C.C([O-])(O)=O.[Na+].C(Cl)Cl>C(O)C.[Zn]>[N:1]1([C:6]2[CH:7]=[CH:8][C:9]([CH2:10][N:11]3[CH2:20][C:19]([CH3:22])([CH3:21])[C:18]4[C:13](=[CH:14][C:15]([NH2:23])=[CH:16][CH:17]=4)[CH2:12]3)=[CH:26][CH:27]=2)[CH:5]=[CH:4][N:3]=[CH:2]1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 6344DichloromethaneHCID 516892Sodium BicarbonateHCID 68194845HCID 68194845, compound

Product 1

HCID 68194936HCID 68194936, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 702EthanolSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of Example 163A (1.45 g, 4.00 mmol) in 95% ethanol (20 mL) were added zinc (2 g, 30.6 mmol) and acetic acid (4 mL, 69.9 mmol). The reaction mixture was stirred for 4 hours at 50° C. Aqueous saturated NaHCO3 solution (200 mL) and CH2Cl2 (200 mL) were added to the reaction mixture and the suspension was filtered. The aqueous layer was extracted with CH2Cl2 (200 mL). The combined organic layers were washed with saturated NaCl (1×300 mL), dried over Na2SO4, filtered, and concentrated. The crude material was purified using the Chemflash system using a 120 g C18 column eluting with 40-80% methanol in water (0.8 g (NH4)2CO3 in 1 L of water) to provide the title compound. LC-MS: m/e=333 (M+H)+. 1H NMR (400 MHz, DMSO-d6), δ 8.25 (s, 1H), 7.73 (s, 1H), 7.62 (d, J=8.4 Hz, 2H), 7.49 (d, J=8.4 Hz, 2H), 7.11 (s, 1H), 6.97 (d, J=8.4 Hz, 1H), 6.41 (dd, J=8.4 Hz, 2.0 Hz, 1H), 6.16 (d, J=2.0 Hz, 1H), 4.76 (s, 2H), 3.62 (s, 2H), 3.43 (s, 2H), 2.31 (s, 2H), 1.15 (s, 6H).

Workup

  1. filtrationthe suspension was filtered
  2. extractionThe aqueous layer was extracted with CH2Cl2 (200 mL)
  3. washThe combined organic layers were washed with saturated NaCl (1×300 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was purified
  8. washeluting with 40-80% methanol in water (0.8 g (NH4)2CO3 in 1 L of water)

Sources & evidence

ORD record
ord-7a4359d0afa54117b537f79b050550f2
Source dataset
uspto-grants-2014_04
Patent number
US08710065B2

Reaction notes

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