Nitric Acid → 3-(4-Difluoromethoxy-phenylazo)-pentane-2,4-dione

HRID 1924481Notes

Reaction equation

HRID 1924481 reaction equation
[F:1][CH:2]([F:11])[O:3][C:4]1[CH:9]=[CH:8][C:7]([NH2:10])=[CH:6][CH:5]=1.P(=O)(O)(O)O.[N+]([O-])(O)=O.[N:21]([O-])=O.[Na+].[CH3:25][C:26](=[O:31])[CH2:27][C:28](=[O:30])[CH3:29].C([O-])(=O)C.[K+].C(=O)([O-])[O-].[Na+].[Na+]>C(O)C>[F:1][CH:2]([F:11])[O:3][C:4]1[CH:5]=[CH:6][C:7]([N:10]=[N:21][CH:27]([C:26](=[O:31])[CH3:25])[C:28](=[O:30])[CH3:29])=[CH:8][CH:9]=1

Participants

9

Reactant 7

HCID 944Nitric AcidHCID 1004Phosphoric AcidHCID 10340Sodium CarbonateHCID 31261AcetylacetoneHCID 517044Potassium AcetateHCID 7373634-(Difluoromethoxy)anilineHCID 23668193Sodium Nitrite

Product 1

HCID 866425423-(4-Difluoromethoxy-phenylazo)-pentane-2,4-dioneYield 102.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
-6 °C

Procedure

A solution of 4-difluoromethoxy-phenylamine (2 g, 13 mmol) was cooled at −6° C. and phosphoric acid (85%, 13 mL) followed by nitric acid (65%, 9 mL) very slowly. When the mixture reached the room temperature it was stirred 15 minutes for complete dissolution. The solution was cooled again to −6° C. and solid sodium nitrite (0.954 g, 13.8 mmol) was added during 5 minutes followed by crushed ice. The reaction mixture was added into a suspension of pentane-2,4-dione (1.32 g, 13.2 mmol) and potassium acetate (24.1 g, 251 mmol) in ethanol (130 mL) at 0° C. Stirring is continued for 15 min at 0-5° C. and an aqueous solution 2M of sodium carbonate is added until the pH is 9-10. The solution is extracted with dichloromethane (4×200 mL). The combined organic layers were washed with water, dried with magnesium sulphate, filtrated and the solvent was removed in the vacuum to obtain 3.6 g (100%) of the final product that was used as a crude on the next step. MS: M=269.1 (M−H)+

Workup

  1. customthe room temperature it
  2. customby crushed ice
  3. stirringStirring
  4. waitis continued for 15 min at 0-5° C.
  5. extractionThe solution is extracted with dichloromethane (4×200 mL)
  6. washThe combined organic layers were washed with water
  7. dry with materialdried with magnesium sulphate
  8. filtrationfiltrated
  9. customthe solvent was removed in the vacuum

Sources & evidence

ORD record
ord-074605a2dfdf40a4aa05223a0c99f8c9
Source dataset
uspto-grants-2012_05
Patent number
US08178538B2

Reaction notes

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