1,8-Diazabicyclo(5.4.0)undec-7-ene → 3-Bromo-5-(methylthio)pyridine

HRID 606810Notes

Reaction equation

HRID 606810 reaction equation
N12CCCN=C1CCCCC2.[Br:12][C:13]1[CH:14]=[N:15][CH:16]=[C:17](I)[CH:18]=1.[CH3:20][S-:21].[Na+]>C1(C)C=CC=CC=1.[Cu](Br)Br>[Br:12][C:13]1[CH:14]=[N:15][CH:16]=[C:17]([S:21][CH3:20])[CH:18]=1

Participants

6

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 8204093-Bromo-5-iodopyridineHCID 4378561Sodium methanethiolate

Product 1

HCID 223903593-Bromo-5-(methylthio)pyridineYield 70%

Reagents, catalysts & solvents 2

HCID 24611Copper bromide (CuBr2)CatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

Add 1,8-diazabicyclo[5.4.0]undec-7-ene (0.8 mL, 5.28 mmol) to a solution of 3-bromo-5-iodopyridine (500 mg, 1.76 mmol), (prepared as described in PREPARATION 21), sodium methanethiolate (370 mg, 5.28 mmol) and copper bromide (50.2 mg, 0.35 mmol) in toluene (3 mL). Stir in a sealed flask at 90° C. overnight and then partition between water and ethyl acetate. Separate the organic layer and wash with an aqueous saturated solution of sodium chloride. Dry (magnesium sulfate), filter and concentrate. Purify the residue by silica gel chromatography, eluting with hexane:ethyl acetate, to give the title compound (250 mg, 70%).

Workup

  1. custompartition between water and ethyl acetate
  2. customSeparate the organic layer
  3. washwash with an aqueous saturated solution of sodium chloride
  4. dry with materialDry (magnesium sulfate)
  5. filtrationfilter
  6. concentrationconcentrate
  7. customPurify the residue by silica gel chromatography
  8. washeluting with hexane

Sources & evidence

ORD record
ord-2183564348404f18bd97fa9e9ac7916e
Source dataset
uspto-grants-2011_03
Patent number
US07915424B2

Reaction notes

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