Dimethylformamide → HCID 22663345, compound

HRID 380414Notes

Reaction equation

HRID 380414 reaction equation
C([C:4]1[C:13]([N+:14]([O-:16])=[O:15])=[C:12]([O:17][CH3:18])[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7])(O)=O.S(Cl)(Cl)=O.C[N:24](C)C=O>C1(C)C=CC=CC=1>[NH2:24][C:4]1[C:13]([N+:14]([O-:16])=[O:15])=[C:12]([O:17][CH3:18])[CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 22663208HCID 22663208, compound

Product 1

HCID 22663345HCID 22663345, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of methyl 2-carboxy-4-methoxy-3-nitrobenzoate (3.43 g, Reference Example 10) was dissolved in toluene (20 ml) was treated with thionyl chloride (1.5 ml) then with dimethylformamide (0.015 ml). The resulting solution was stirred at reflux for 1 hour then cooled to room temperature and then evaporated. The residue was dissolved in acetone (20 ml) and added to a solution of sodium azide (1.3 g) in water (20 ml) cooled in an ice bath. The mixture was stirred for 1 hour then diluted with water. The resulting precipitate was collected by filtration. This solid was dissolved in a mixture of t-butanol and water (20 ml, 9:1) and gradually warmed to reflux and held at this temperature for 1 hour. The solution was cooled to room temperature and then evaporated. The residue was subjected to flash chromatography on silica to give the title compound (1.8 g). M+H 227. NMR ((CD3)2SO): δ 3.82 (s,3H), 3.90(s,3H), 6.53(d,J=8 Hz,1H), 7.1(bs,2H), 7.96(d,J=8 Hz,1H).

Workup

  1. temperatureat reflux for 1 hour
  2. customevaporated
  3. dissolutionThe residue was dissolved in acetone (20 ml)
  4. additionadded to a solution of sodium azide (1.3 g) in water (20 ml)
  5. temperaturecooled in an ice bath
  6. stirringThe mixture was stirred for 1 hour
  7. additionthen diluted with water
  8. filtrationThe resulting precipitate was collected by filtration
  9. dissolutionThis solid was dissolved in a mixture of t-butanol and water (20 ml, 9:1)
  10. temperaturegradually warmed
  11. temperatureto reflux
  12. temperatureThe solution was cooled to room temperature
  13. customevaporated

Sources & evidence

ORD record
ord-31edf74078b14e1ab7455fc19acb5733
Source dataset
uspto-grants-2001_10
Patent number
US06303600B1

Reaction notes

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