Azobisisobutyronitrile → HCID 68546115, compound

HRID 1446692Notes

Reaction equation

HRID 1446692 reaction equation
[C:1]([C:5]1[CH:10]=[C:9]([CH3:11])[CH:8]=[C:7]([I:12])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].C1C(=O)N(Br)C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C.[NH:33]1[CH2:38][CH2:37][O:36][CH2:35][CH2:34]1>C(Cl)(Cl)(Cl)Cl>[C:1]([C:5]1[CH:10]=[C:9]([CH:8]=[C:7]([I:12])[CH:6]=1)[CH2:11][N:33]1[CH2:38][CH2:37][O:36][CH2:35][CH2:34]1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 8083MorpholineHCID 67184N-bromobutanimideHCID 10891057HCID 10891057, compound

Product 1

HCID 68546115HCID 68546115, compound

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
70 °C

Procedure

Dissolve 1-tert-butyl-3-iodo-5-methyl-benzene (1 g, 3.6 mmol, prepared according to Chem. Soc. Perkin Trans. I, 1987, page 859-866) in carbon tetrachloride (20 mL) under nitrogen. Add NBS (0.71 g, 1.1 equiv.) followed by AIBN (0.06 g, 0.1 equiv.) and heat overnight at 70° C. Filter in the morning, washing with hexanes. Concentrate filtrate and use crude. Dissolve this residue in THF (10 mL) under nitrogen and cool to 0° C. Add morpholine (0.64 mL, 2 equiv.) dropwise via syringe and stir 5 minutes with cooling. Remove ice bath and let warm to room temperature. After one hour concentrate to dryness and purify the residue on silica gel (Hexanes→4:1 Hexanes Ethyl Acetate) to give product (0.785 g, 60% over 2 steps). MS (ES), m/z 360.1 (M+1).

Workup

  1. filtrationFilter in the morning
  2. washwashing with hexanes
  3. dissolutionDissolve this residue in THF (10 mL) under nitrogen
  4. temperaturecool to 0° C
  5. temperaturewith cooling
  6. temperatureRemove ice bath and let warm to room temperature
  7. concentrationAfter one hour concentrate to dryness
  8. custompurify the residue on silica gel (Hexanes→4:1 Hexanes Ethyl Acetate)
  9. customto give product (0.785 g, 60% over 2 steps)

Sources & evidence

ORD record
ord-521a0c1ed38a43b78f3d7eaea4d36312
Source dataset
uspto-grants-2010_02
Patent number
US07666879B2

Reaction notes

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