Hydrochloric Acid → (R)-3-(2-Chloro-4-nitro-1H-imidazol-1-yl)-2-methylpropane-1,2-diol

HRID 856151Notes

Reaction equation

HRID 856151 reaction equation
[Cl:1][C:2]1[NH:3][CH:4]=[C:5]([N+:7]([O-:9])=[O:8])[N:6]=1.[N+](C1C=CC(C([O:19][CH2:20][C@@:21]2([CH3:24])[CH2:23][O:22]2)=O)=CC=1)([O-])=O.C(N(CC)CC)C.C(=O)([O-])[O-].[K+].[K+].Cl.S([O-])([O-])(=O)=O.[Mg+2]>C(OCC)(=O)C>[Cl:1][C:2]1[N:3]([CH2:23][C@:21]([OH:22])([CH3:24])[CH2:20][OH:19])[CH:4]=[C:5]([N+:7]([O-:9])=[O:8])[N:6]=1

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 11430Potassium CarbonateHCID 24083Sulfuric acid magnesium salt (1:1)HCID 13779866(2R)-(-)-2-Methylglycidyl 4-nitrobenzoateHCID 178526855HCID 178526855, compound

Product 1

HCID 16099121(R)-3-(2-Chloro-4-nitro-1H-imidazol-1-yl)-2-methylpropane-1,2-diolYield 92%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

2-Chloro-4-nitro-1H-imidazole (600 g, 4.07 mol) and (R)-2-methyloxiran-2-ylmethyl 4-nitrobenzoate (1060 g, 4.47 mol) were dissolved in ethyl acetate (2124 ml), triethylamine (113.64 ml, 0.82 mol) was added to the solution, and the resulting mixture was stirred under reflux for 16 hours. The reaction mixture was concentrated under reduced pressure, and ethyl acetate (530 ml) and toluene (5300 ml) were added to the residue. The resulting precipitates were filtered off and dissolved in methanol (10.6 1). Potassium carbonate (55.4 g, 0.4 mol) was added to the solution, the resulting mixture was stirred at room temperature for 1 hour, concentrated hydrochloric acid (66 ml) and magnesium sulfate (671 g) were added in this order with cooling on ice-bath, and the resulting mixture was stirred for 30 minutes. Insoluble matters were removed by filtration, and the filtrate was concentrated under reduced pressure. To the residue, ethyl acetate (530 ml) and toluene (5300 ml) were added. The resulting precipitates were filtered off and dried at 50° C. to afford (R)-2-chloro-1-(2,3-dihydroxy-2-methylpropyl)-4-nitroimidazole (879.1 g, yield 92%) as a light brown powder.

Workup

  1. temperatureunder reflux for 16 hours
  2. concentrationThe reaction mixture was concentrated under reduced pressure, and ethyl acetate (530 ml) and toluene (5300 ml)
  3. additionwere added to the residue
  4. customThe resulting precipitates
  5. filtrationwere filtered off
  6. dissolutiondissolved in methanol (10.6 1)
  7. stirringthe resulting mixture was stirred at room temperature for 1 hour
  8. temperaturewith cooling on ice-bath
  9. stirringthe resulting mixture was stirred for 30 minutes
  10. customInsoluble matters were removed by filtration
  11. concentrationthe filtrate was concentrated under reduced pressure
  12. additionTo the residue, ethyl acetate (530 ml) and toluene (5300 ml) were added
  13. customThe resulting precipitates
  14. filtrationwere filtered off
  15. customdried at 50° C.

Sources & evidence

ORD record
ord-3eca78db7bf94f399b0d6454877df6b7
Source dataset
uspto-grants-2007_08
Patent number
US07262212B2

Reaction notes

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