Carbon Tetrachloride → Pyridine, 2-(bromomethyl)-5-(2,2,2-trifluoroethoxy)-

HRID 2041189Notes

Reaction equation

HRID 2041189 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][C:10]([F:13])([F:12])[F:11])=[CH:4][N:3]=1.C1C(=O)N([Br:21])C(=O)C1.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.C(Cl)(Cl)(Cl)Cl>C(Cl)Cl>[Br:21][CH2:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][C:10]([F:11])([F:13])[F:12])=[CH:4][N:3]=1

Participants

6

Reactant 4

HCID 5943Carbon TetrachlorideHCID 7187Benzoyl Peroxide2×HCID 67184N-bromobutanimide2×HCID 235684332-Methyl-5-(2,2,2-trifluoroethoxy)pyridine

Product 1

HCID 57655951Pyridine, 2-(bromomethyl)-5-(2,2,2-trifluoroethoxy)-Yield 13%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

Add 2-methyl-5-(2,2,2-trifluoroethoxy)-pyridine (2.5 g, 13.1 mmol), NBS (2.3 g, 13.1 mmol) and benzoyl peroxide (50 mg) to a flask containing carbon tetrachloride (30 mL). Heat the mixture at 80° C. in a sealed flask for 16 h. Cool the flask, add NBS (1.1 g, 6.5 mmol) and benzoyl peroxide (100 mg), then continue heating at 80° C. for an additional 5 h. Cool the mixture, dilute with DCM, then wash with saturated sodium bisulfite (10 mL). Collect the organic layer and concentrate in vacuo. Purify by chromatography on silica gel eluting with hexane/EtOAc (9:1) to obtain the desired intermediate (460 mg, 13%).

Workup

  1. temperatureCool the flask
  2. temperaturecontinue heating at 80° C. for an additional 5 h
  3. temperatureCool the mixture
  4. washwash with saturated sodium bisulfite (10 mL)
  5. customCollect the organic layer
  6. concentrationconcentrate in vacuo
  7. customPurify by chromatography on silica gel eluting with hexane/EtOAc (9:1)

Sources & evidence

ORD record
ord-674dfd0ba1844542866a3eaa2c56b8ac
Source dataset
uspto-grants-2013_11
Patent number
US08580780B2

Reaction notes

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