Dimethylformamide → HCID 67104421, compound

HRID 1157113Notes

Reaction equation

HRID 1157113 reaction equation
[CH3:1][C:2]1[CH:10]=[CH:9][C:5]([C:6](O)=O)=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].CN(C)C=[O:17].S(Cl)(Cl)=O.[CH2:23]([NH:26][CH2:27][CH2:28][CH3:29])[CH2:24][CH3:25]>C(OCC)(=O)C.C1(C)C=CC=CC=1>[CH2:23]([N:26]([CH2:27][CH2:28][CH3:29])[C:1](=[O:17])[C:2]1[CH:10]=[CH:9][C:5]([CH3:6])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12])[CH2:24][CH3:25]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 73194-Methyl-3-nitrobenzoic acidHCID 8902DipropylamineHCID 24386Thionyl Chloride

Product 1

HCID 67104421HCID 67104421, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

To a mixture of 4-methyl-3-nitrobenzoic acid (36.23 g, 0.2 mmol), N,N-dimethylformamide (5 mL), and toluene (85 mL) was added with stirring thionyl chloride (30 mL, 48.8 g, 0.41 mole). The mixture was stirred at gentle reflux for four hours, then distilled to approximately half the volume (67.77 g residual net weight) to remove excess thionyl chloride. This solution was cooled to 20° C., and 22.6 grams of it (nominally 6.67 mmol) was added to a solution of N,N-di-n-propylamine (22.0 g, 0.22 mole) in ethyl acetate (100 mL) resulting in immediate formation of a slurry that was stirred at ambient temperature overnight. This was then quenched into water (150 mL). The organic layer was washed with cold 0.5 N hydrochloric acid (100 mL), then with 5% aqueous sodium bicarbonate, dried (MgSO4) and evaporated to give a colorless oil weighing 16.55 g (94.0%). This was characterized by proton and carbon nmr, as well as electrospray mass spectrum (M+1 at m/e 265.1).

Workup

  1. temperatureat gentle reflux for four hours
  2. distillationdistilled to approximately half the volume (67.77 g residual net weight)
  3. customto remove excess thionyl chloride
  4. customresulting in immediate formation of a slurry that
  5. stirringwas stirred at ambient temperature overnight
  6. customThis was then quenched into water (150 mL)
  7. washThe organic layer was washed with cold 0.5 N hydrochloric acid (100 mL)
  8. dry with materialwith 5% aqueous sodium bicarbonate, dried (MgSO4)
  9. customevaporated
  10. customto give a colorless oil

Sources & evidence

ORD record
ord-a2496f572bbd4050a26d094ccc4f05c3
Source dataset
uspto-grants-2010_10
Patent number
US07807607B2

Reaction notes

Loading…