Azobisisobutyronitrile → HCID 86725338, compound

HRID 925227Notes

Reaction equation

HRID 925227 reaction equation
[Br:1][C:2]1[C:3]([O:20][CH2:21][CH:22]=[CH:23][CH3:24])=[C:4](I)[C:5]2[CH2:11][CH2:10][N:9]([C:12](=[O:17])[C:13]([F:16])([F:15])[F:14])[CH2:8][CH2:7][C:6]=2[CH:18]=1.[PH2](O)=O.CC(N=NC(C#N)(C)C)(C#N)C>CCO>[Br:1][C:2]1[C:3]2[O:20][CH2:21][CH:22]([CH2:23][CH3:24])[C:4]=2[C:5]2[CH2:11][CH2:10][N:9]([C:12](=[O:17])[C:13]([F:16])([F:15])[F:14])[CH2:8][CH2:7][C:6]=2[CH:18]=1

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 4124402Phosphinic AcidHCID 131735005HCID 131735005, compound

Product 1

HCID 86725338HCID 86725338, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
90 °C

Procedure

Into a 100 ml flask containing the product of step (g) (642 mg, 1.24 mmol) dissolved in EtOH (20 ml), TEA (1.7 ml, 12.4 mmol), hypophosphorous acid (2.3 ml, 12.4 mmol), and AIBN (407 mg, 2.48 mmol) were added. The reaction mixture was heated to 90° C. for 30 minutes, and then the volatiles were evaporated in vacuo. The resulting residue was diluted with water (100 ml) and extracted with DCM (3×). The combined DCM extracts were washed with brine, dried over Na2SO4, and solvent evaporated in vacuo to give the crude product. Purification by silica-gel chromatography (gradient elution: 0 to 30% EtOAc in hexanes) gave the sub-title compound as a white solid that was contaminated with AIBN. This material was used as obtained in the next step. MS: ESI (positive): 392, 394 (M+H).

Workup

  1. customthe volatiles were evaporated in vacuo
  2. additionThe resulting residue was diluted with water (100 ml)
  3. extractionextracted with DCM (3×)
  4. washThe combined DCM extracts were washed with brine
  5. dry with materialdried over Na2SO4, and solvent
  6. customevaporated in vacuo
  7. customto give the crude product
  8. customPurification
  9. washby silica-gel chromatography (gradient elution: 0 to 30% EtOAc in hexanes)

Sources & evidence

ORD record
ord-8033803d492746f8b06b07de98625bf6
Source dataset
uspto-grants-2016_03
Patent number
US09284277B2

Reaction notes

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