3-Hydroxybenzophenone → HCID 71093086, compound

HRID 877343Notes

Reaction equation

HRID 877343 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([C:8]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=O)[CH:5]=[CH:6][CH:7]=1.Cl.[NH2:17]O.C([O-])(=O)C.[Na+].C([O-])(=O)C.[NH4+]>CO.C(O)C.N.[Zn]>[NH2:17][CH:8]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:4]1[CH:3]=[C:2]([OH:1])[CH:7]=[CH:6][CH:5]=1

Participants

9

Reactant 4

HCID 830503-HydroxybenzophenoneHCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 517165Ammonium Acetate

Product 1

HCID 71093086HCID 71093086, compound

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 222AmmoniaSolventHCID 702EthanolSolventHCID 887MethanolSolvent

Procedure

(3-Hydroxyphenyl)(phenyl)methanone (400 g, 2 mol) was dissolved in methanol (4 L). Hydroxylamine hydrochloride (168 g, 2.4 mol) and sodium acetate (331 g, 4 mol) were added to the resulting solution. The mixture was heated at reflux for 18 hours. After cooling to RT solvent was evaporated at reduced pressure, then water (3 L) was added to the residue. The product was extracted with ethyl acetate (3×3 L). The combined organic extracts were washed with saturated aqueous sodium hydrogen carbonate, brine, dried (sodium sulfate), filtered and the solvent evaporated at reduced pressure. The crude residue (1085 g) was used in the next step without purification. The crude oxime, 362 g, (287 g, 1.3 mol of pure oxime based on analysis) was dissolved in ethanol (860 mL) and 25% aqueous ammonia (3000 mL). To this mixture ammonium acetate (52 g, 0.7 mol) was added followed by portion wise addition of zinc powder (440 g, 6.7 mol) to maintain an internal not exceeding 40° C. The mixture was stirred without heating for 18 hours then filtered through a pad of celite. The filter cake was washed with ethyl acetate. The filtrate was collected and the formed layers were separated. The aqueous layer was extracted with ethyl acetate (5×5 L). The combined organic extracts layers were washed with brine (×2) and the solvent was evaporated at reduced pressure. The product was dried in vacuo (35° C., 18 hours).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 18 hours
  3. customwas evaporated at reduced pressure
  4. additionwater (3 L) was added to the residue
  5. extractionThe product was extracted with ethyl acetate (3×3 L)
  6. washThe combined organic extracts were washed with saturated aqueous sodium hydrogen carbonate, brine
  7. dry with materialdried (sodium sulfate)
  8. filtrationfiltered
  9. customthe solvent evaporated at reduced pressure
  10. customThe crude residue (1085 g) was used in the next step without purification
  11. temperatureto maintain an internal not
  12. customexceeding 40° C
  13. temperaturewithout heating for 18 hours
  14. filtrationthen filtered through a pad of celite
  15. washThe filter cake was washed with ethyl acetate
  16. customThe filtrate was collected
  17. customthe formed layers were separated
  18. extractionThe aqueous layer was extracted with ethyl acetate (5×5 L)
  19. washThe combined organic extracts layers were washed with brine (×2)
  20. customthe solvent was evaporated at reduced pressure
  21. customThe product was dried in vacuo (35° C., 18 hours)

Sources & evidence

ORD record
ord-57164a0f26da496796995a9b2e2b938e
Source dataset
uspto-grants-2015_03
Patent number
US08987299B2

Reaction notes

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