m-Nitroacetophenone → HCID 53729690, compound

HRID 1703780Notes

Reaction equation

HRID 1703780 reaction equation
P(Cl)(Cl)([Cl:3])=O.[N+:6]([C:9]1[CH:10]=[C:11]([C:15](=O)[CH3:16])[CH:12]=[CH:13][CH:14]=1)([O-:8])=[O:7].[C:18](=[O:21])(O)[O-].[Na+]>CN(C)C=O>[N+:6]([C:9]1[CH:10]=[C:11]([CH:12]=[CH:13][CH:14]=1)[C:15]([Cl:3])=[CH:16][CH:18]=[O:21])([O-:8])=[O:7]

Participants

5

Reactant 3

HCID 8494m-NitroacetophenoneHCID 24813Phosphorus oxychlorideHCID 516892Sodium Bicarbonate

Product 1

HCID 53729690HCID 53729690, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To 400 ml of anhydrous dimethylformamide was added with stirring 455 g. (3.01 moles) of phosphorus oxychloride. The mixture was kept at 20° to 25° throughout the addition by external cooling. After standing overnight, a solution of 330 g. (2 moles) of m-nitroacetophenone in 400 ml anhydrous dimethylformamide was added dropwise, keeping the pot temperature at 20° to 25° by external cooling. Addition required about 1/2 hour. Stirring was continued without external cooling, during which time the temperature rose to 55° C. and then dropped to ambient temperature. The mixture was poured into cold sodium bicarbonate solution, keeping the pH at least 7, and the crude product was filtered. This product was taken up in ca. 1 liter of benzene and separated from residual water entrained by the crystals by drying with anhydrous potassium carbonate. The benzene solution was concentrated on a rotary evaporator to approximately one-third of its volume, and hexane was added until the hot solution just began to cloud. A small amount of benzene dissolved some material that oiled out, and the solution was cooled to yield crystals m.p. 83°. A second crop was obtained by evaporation of the filtrate and cooling. Total yield 195.7 g. (46.4%).

Workup

  1. additionThe mixture was kept at 20° to 25° throughout the addition by external cooling
  2. customat 20° to 25°
  3. additionAddition required about 1/2 hour
  4. stirringStirring
  5. customrose to 55° C.
  6. additiondropped to ambient temperature
  7. filtrationthe crude product was filtered
  8. customseparated from residual water
  9. dry with materialby drying with anhydrous potassium carbonate
  10. concentrationThe benzene solution was concentrated on a rotary evaporator to approximately one-third of its volume, and hexane
  11. additionwas added until the hot solution
  12. dissolutionA small amount of benzene dissolved some material
  13. temperaturethe solution was cooled

Sources & evidence

ORD record
ord-6c27b292c6a145189c2a13544b81da5d
Source dataset
uspto-grants-1978_11
Patent number
US04125563

Reaction notes

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