Iron → Fe Ac2O AcOH

HRID 1399444Notes

Reaction equation

HRID 1399444 reaction equation
[F-].[K+].[N+](C1C=CC=C([N+]([O-])=O)[C:7]=1[C:8]([OH:10])=[O:9])([O-])=O.[CH2:18]1OCCOCCOCCOCCOCC[O:20][CH2:19]1.[Fe:36]>CS(C)=O.CC(O)=O.CC(OC(C)=O)=O.CCOC(C)=O>[Fe:36].[CH3:18][C:19]([O:10][C:8]([CH3:7])=[O:9])=[O:20].[CH3:7][C:8]([OH:10])=[O:9]

Participants

9

Reactant 4

HCID 23925IronHCID 2855718-Crown-6HCID 119206Benzoic acid, 2,6-dinitro-HCID 522689Potassium Fluoride

Product 1

HCID 86713117Fe Ac2O AcOHYield 34%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 679Dimethyl SulfoxideSolventHCID 7918Acetic AnhydrideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
175 °C

Procedure

A mixture of spray-dried KF (1.07 g, 18.58 mmol), intermediate 2 (500 mg, 1.858 mmol) and catalytic amount of 18-crown-6 in dry DMSO (8 mL) was stirred at 170-180° C. for 30 min. Work-up of the reaction mixture as described in example 1 gave the residue. This residue was dissolved in a mixture of AcOH and Ac2O (12 mL, 1:1) and added iron powder (2.08 g, 37.17 mmol) at rt. The mixture was stirred at 60-70° C. for 30 min and diluted with EtOAc (25 mL). Filtered the solution to remove iron powder and washed with few mL of EtOAc. Ethyl acetate was removed under reduced pressure. The residue was chromatographed over silica gel column using chloroform:methanol (70:30) as eluents to give the product as a white color solid (160 mg, 34%), mp 240-242° C. 1H NMR (400 MHz, DMSO-d6): δ 10.51 (1H, s, exchangeable with D2O), 7.82 (1H, br s, exchangeable with D2O), 7.76 (1H, t, J=8.6 Hz), 7.70 (1H, d, J=14.0 Hz), 7.34 (1H, d, J=8.4 Hz), 3.71 (2H, s), 2.08 (3H, s); LC-MS (negative ion mode): m/z 253 (M−H)−.

Workup

  1. customgave the residue
  2. stirringThe mixture was stirred at 60-70° C. for 30 min
  3. filtrationFiltered the solution
  4. customto remove iron powder
  5. washwashed with few mL of EtOAc
  6. customEthyl acetate was removed under reduced pressure
  7. customThe residue was chromatographed over silica gel column

Sources & evidence

ORD record
ord-edcb94980fb9431889bf5387d602e47b
Source dataset
uspto-grants-2014_12
Patent number
US08906344B2

Reaction notes

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