3-Bromo-2-methyl-1-propene → 2-Chloro-5-iodo-N-(2-methyl-2-propen-1-yl)-4-pyridinamine

HRID 1475351Notes

Reaction equation

HRID 1475351 reaction equation
[CH3:1][C:2]([CH3:5])([O-])[CH3:3].[K+].[Cl:7][C:8]1[CH:13]=[C:12]([NH2:14])[C:11]([I:15])=[CH:10][N:9]=1.BrCC(C)=C>C1COCC1>[Cl:7][C:8]1[CH:13]=[C:12]([NH:14][CH2:1][C:2]([CH3:5])=[CH2:3])[C:11]([I:15])=[CH:10][N:9]=1

Participants

5

Reactant 3

HCID 3577853-Bromo-2-methyl-1-propeneHCID 23665647Potassium tert-butoxideHCID 454803662-Chloro-5-iodopyridin-4-amine

Product 1

HCID 867239682-Chloro-5-iodo-N-(2-methyl-2-propen-1-yl)-4-pyridinamineYield 76%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Potassium tert-butoxide (4.56 g, 40.73 mmol) was added to a stirred solution of 2-chloro-5-iodo-pyridin-4-ylamine (8.62 g, 33.94 mmol) in anhydrous THF (140 mL) and the mixture was stirred at room temperature for 0.25 h. 3-Bromo-2-methyl-propene (5.51 g, 40.73 mmol) was added and the mixture was stirred at room temperature overnight. The solvent was removed in vacuo and the residues partitioned between DCM (100 mL) and water (100 mL). The organic layer was separated, the solvent removed in vacuo and the residues subjected to column chromatography on silica. Gradient elution with 5-20% EtOAc in petrol afforded the title compound (7.93 g, 76%) as a pale yellow oil. 1H NMR (DMSO-d6) 8.24 (1H, s), 6.50 (1H, br t), 6.39 (1H, s), 4.84 (1H, d), 4.73 (1H, d), 3.83 (2H, d), 1.70 (3H, s). MS: [M+H]+ 309.

Workup

  1. stirringthe mixture was stirred at room temperature overnight
  2. customThe solvent was removed in vacuo
  3. customthe residues partitioned between DCM (100 mL) and water (100 mL)
  4. customThe organic layer was separated
  5. customthe solvent removed in vacuo
  6. washGradient elution with 5-20% EtOAc in petrol

Sources & evidence

ORD record
ord-06ab7c047b5d4e0598be26ecf0ae788c
Source dataset
uspto-grants-2015_04
Patent number
US09018214B2

Reaction notes

Loading…