1,3-Dibromo-5,5-dimethylhydantoin → 5-bromo-1,4-dimethyl-6-octyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine

HRID 60406Notes

Reaction equation

HRID 60406 reaction equation
[CH3:1][N:2]1[C:6]2=[N:7][C:8]([CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])=[CH:9][C:10]([CH3:11])=[C:5]2[CH2:4][CH2:3]1.[Br:20]N1C(C)(C)C(=O)N(Br)C1=O>C(Cl)(Cl)Cl>[Br:20][C:9]1[C:10]([CH3:11])=[C:5]2[CH2:4][CH2:3][N:2]([CH3:1])[C:6]2=[N:7][C:8]=1[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19]

Participants

4

Reactant 2

HCID 64791,3-Dibromo-5,5-dimethylhydantoinHCID 716787341,4-dimethyl-6-octyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 716787355-bromo-1,4-dimethyl-6-octyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Conditions

Temperature
0 °C

Procedure

To a solution containing 402 mg (1.54 mmol) of 1,4-Dimethyl-6-octyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine in 6 mL of chloroform was added 220 mg (0.77 mmol) of 1,3-dibromo-5,5-dimethylhydantoin in five portions at 0° C. The reaction mixture was stirred at 0° C. for 30 min. The reaction mixture was quenched by the addition of 8 mL of sat aq. NaHCO3. The mixture was extracted with three 25-mL portions of chloroform. The combined organic layer was washed with brine, dried over anhydrous MgSO4, filtered, and concentrated under diminished pressure. The residue was purified via flash chromatography on a silica gel column (43×2.5 cm). Step gradient elution with 1:10 ethyl acetate-hexanes as eluent gave 5-bromo-1,4-dimethyl-6-octyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine as a yellow oil: yield 371 mg (71%); silica gel TLC Rf 0.65 (8:1:1 hexanes-ethyl acetate-methanol); 1H NMR (CDCl3) δ 0.81 (t, 2H, J=7.2 Hz), 1.16-1.30 (m, 10H), 1.65 (quint, 2H, J=8.0 Hz), 2.12 (s, 3H), 2.59 (t, 2H, J=8.0 Hz), 2.79-2.85 (m, 5H), 3.41 (t, 2H, J=8.0 Hz).

Workup

  1. customThe reaction mixture was quenched by the addition of 8 mL of sat aq. NaHCO3
  2. extractionThe mixture was extracted with three 25-mL portions of chloroform
  3. washThe combined organic layer was washed with brine
  4. dry with materialdried over anhydrous MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under diminished pressure
  7. customThe residue was purified via flash chromatography on a silica gel column (43×2.5 cm)
  8. washStep gradient elution with 1:10 ethyl acetate-hexanes as eluent

Sources & evidence

ORD record
ord-28f25d22d1de425f91bea64869000f4b
Source dataset
uspto-grants-2016_09
Patent number
US09440967B2

Reaction notes

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