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

HRID 60392

Reaction equation

HRID 60392 reaction equation
[CH3:1][N:2]1[C:6]2=[N:7][C:8]([CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])=[CH:9][C:10]([CH3:11])=[C:5]2[CH2:4][CH2:3]1.[Br:17]N1C(C)(C)C(=O)N(Br)C1=O>C(Cl)(Cl)Cl>[Br:17][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][CH3:16]

Participants

4

Reactant 2

HCID 64791,3-Dibromo-5,5-dimethylhydantoinHCID 716778951,4-Dimethyl-6-pentyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 716778965-Bromo-1,4-dimethyl-6-pentyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 108 mg (0.50 mmol) of 1,4-dimethyl-6-pentyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine in 3 mL of chloroform was added 70.7 mg (0.25 mmol) of 1,3-dibromo-5,5-dimethylhydantoin in portions at 0° C. The reaction mixture was stirred at 0° C. for 30 min. The reaction was quenched by the addition of 5 mL of sat aq. NaHCO3. The mixture was extracted with chloroform and the combined organic layer was washed with brine and dried over MgSO4. The concentrated residue was purified by flash chromatography on a silica gel column (20 1.7 cm). Elution with 100:1 hexanes/ethyl acetate gave the product as a yellow oil: yield 136 mg (92%); silica gel TLC Rf 0.65 (8:1:1 hexanes/ethyl acetate/methanol); 1H NMR (CDCl3) δ 0.89 (t, 3H, J=7.2 Hz), 1.33-1.38 (m, 4H), 1.66 (quint, 2H, J=7.6 Hz), 2.16 (s, 3H), 2.77 (t, 2H, J=8.0 Hz), 2.82-2.87 (m, 5H) and 3.40 (t, 2H, J=8.0 Hz); 13C NMR (CDCl3) δ 14.1, 19.5, 22.6, 25.2, 28.4, 31.8, 33.0, 38.1, 52.4, 110.9, 120.4, 141.1, 156.8 and 161.8; mass spectrum, m/z 297.1 and 299.1 (M+H)+ (theoretical 297.1 and 299.1); mass spectrum (APCI), m/z 297.0968 and 199.0937 (M+H)+ (C14H22N2Br requires 297.0966 and 299.0946).

Workup

  1. customThe reaction was quenched by the addition of 5 mL of sat aq. NaHCO3
  2. extractionThe mixture was extracted with chloroform
  3. washthe combined organic layer was washed with brine
  4. dry with materialdried over MgSO4
  5. customThe concentrated residue was purified by flash chromatography on a silica gel column (20 1.7 cm)
  6. washElution with 100:1 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-76650830d7814242b9f83fe6dccc83c5
Source dataset
uspto-grants-2016_09
Patent number
US09440967B2

Linked notes

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