Acetic Acid → HCID 86646540, compound

HRID 2387231Notes

Reaction equation

HRID 2387231 reaction equation
[Cl:1][C:2]1[N:3]=[N:4][C:5]([Cl:12])=[CH:6][C:7]=1[C:8]([F:11])([F:10])[F:9].[C:13](O)(=O)C.OS(O)(=O)=O.S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+].[NH4+].[OH-].[NH4+]>O.[N+]([O-])([O-])=O.[Ag+]>[Cl:12][C:5]1[N:4]=[N:3][C:2]([Cl:1])=[C:7]([C:8]([F:9])([F:10])[F:11])[C:6]=1[CH3:13]

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 1118Sulfuric AcidHCID 14923Ammonium HydroxideHCID 62648Ammonium PersulfateHCID 468472073,6-Dichloro-4-(trifluoromethyl)pyridazine

Product 1

HCID 86646540HCID 86646540, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent3×

Conditions

Temperature
50 °C

Procedure

To a stirred suspension of Preparative Example 3, C4 (1.0 eq) and AgNO3(0.5 eq.) in H2O (0.15M) was added acetic acid (2.0 eq.). The mixture was heated to 50° C. and then a solution of conc. H2SO4(3.0 eq.) in H2O (0.5M) was added to the mixture. The temperature was then raised to 70° C. and a solution of ammonium persulfate (3.0 eq.) in H2O (0.5M) was added dropwise over 10 min. The reaction mixture was heated at 70-75° C. for a further 30 min. After cooling, the reaction mixture was adjusted to pH=7 with 32% ammonium hydroxide solution, and extracted with Et2O. The extracts were washed with brine, dried (Na2SO4) and the solvent was removed under reduced pressure. Crude product was purified by flash column chromatography on silica gel using 2-10% Et2O/Petroleum ether, the desired D1 as a yellow oil (87% yield). 1H-NMR (300 MHz, CDCl3, 300K) δ 2.66 (3H, s). MS (ES) C6H3Cl2F3N2 requires: 231; 233, found: 232; 234 (M+H)+.

Workup

  1. temperatureThe temperature was then raised to 70° C.
  2. temperatureThe reaction mixture was heated at 70-75° C. for a further 30 min
  3. temperatureAfter cooling
  4. extractionextracted with Et2O
  5. washThe extracts were washed with brine
  6. dry with materialdried (Na2SO4)
  7. customthe solvent was removed under reduced pressure
  8. customCrude product was purified by flash column chromatography on silica gel using 2-10% Et2O/Petroleum ether

Sources & evidence

ORD record
ord-64ed3c85a2754821afcc072dda046b48
Source dataset
uspto-grants-2012_09
Patent number
US08268827B2

Reaction notes

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