Hydrochloric Acid → HCID 59771105, compound

HRID 987401Notes

Reaction equation

HRID 987401 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7](F)=[CH:6][C:5]=1[N+:11]([O-:13])=[O:12])([O-:3])=[O:2].[CH3:14][O:15][C:16]([C:18]1[N:19]=[CH:20][NH:21][CH:22]=1)=[O:17].[H-].[Na+].Cl>C1COCC1.C1(C)C=CC=CC=1>[CH3:14][O:15][C:16]([C:18]1[N:19]=[CH:20][N:21]([C:7]2[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[C:5]([N+:11]([O-:13])=[O:12])[CH:6]=2)[CH:22]=1)=[O:17]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 2986753,4-DinitrofluorobenzeneHCID 178418785HCID 178418785, compound

Product 1

HCID 59771105HCID 59771105, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred, 0° C. solution of 1,2-dinitro-4-fluorobenzene (325 mg, 1.74 mmole) and methyl-4-imidazolecarboxylate (200 mg, 1.59 mmole) in THF (5 mL) was added NaH (70 mg, 1.74 mmole) in one portion. The resulting mixture was stirred at 0° C. for 3 hours, then diluted with toluene and acidified with 6N HCl. The phases were separated and the aqueous phase washed with toluene, cooled to 0° C., and basified with conc. NH4OH. Ethyl acetate was added and the resulting mixture stirred until all solids dissolved. Phases separated, organic phase washed with brine, dried over Na2SO4, filtered, concentrated in vacuo. The mixture of regioisomers were separated and purified via flash chromatography (silica gel, 5%→>20% ethanol/ethyl acetate gradient) to fford the desired adduct 19 (225 mg, 48%) as an off-white solid. 1H NMR (500 MHz, dmso d6): 8.41 (1H, d); 8.13 (1H, d); 7.5 (1H, broad s); 7.28 (1H, s); 7.02 (1H, d); 3.80 (3H, s)

Workup

  1. customThe phases were separated
  2. washthe aqueous phase washed with toluene
  3. temperaturecooled to 0° C.
  4. additionEthyl acetate was added
  5. stirringthe resulting mixture stirred until all solids
  6. dissolutiondissolved
  7. customPhases separated
  8. washorganic phase washed with brine
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. additionThe mixture of regioisomers
  13. customwere separated
  14. custompurified via flash chromatography (silica gel, 5%→>20% ethanol/ethyl acetate gradient)

Sources & evidence

ORD record
ord-e7019a9e011c47cd9e674c6d3dda64e4
Source dataset
uspto-grants-2003_10
Patent number
US06632809B2

Reaction notes

Loading…