Methanol → 3-[3-(Tri-n-butylstannanyl)phenyl]pyridine

HRID 985510Notes

Reaction equation

HRID 985510 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=2)[CH:5]=[CH:6][CH:7]=1.C([Li])(C)(C)C.[CH2:19]([Sn:23](Cl)([CH2:28][CH2:29][CH2:30][CH3:31])[CH2:24][CH2:25][CH2:26][CH3:27])[CH2:20][CH2:21][CH3:22].CO>O1CCCC1.C(N(CC)CC)C>[CH2:28]([Sn:23]([CH2:19][CH2:20][CH2:21][CH3:22])([CH2:24][CH2:25][CH2:26][CH3:27])[C:2]1[CH:3]=[C:4]([C:8]2[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=2)[CH:5]=[CH:6][CH:7]=1)[CH2:29][CH2:30][CH3:31]

Participants

7

Reactant 4

HCID 887MethanolHCID 15096Tributyltin ChlorideHCID 131504013-(3-Bromophenyl)pyridineHCID 178418306HCID 178418306, compound

Product 1

HCID 225070873-[3-(Tri-n-butylstannanyl)phenyl]pyridineYield 82%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

A cooled (−78° C.) solution of 3-(3-bromophenyl)pyridine (7.50 g, 32 mmol) in tetrahydrofuran (120 ml) was treated with a cooled (−78° C.) solution of tert-butyllithium (41 ml of a 1.7M solution in hexanes, 70 mmol). After 5 minutes tri-n-butyltin chloride (9.6 ml) was added and the mixture was allowed to warm to room temperature over 1 h. Methanol (7.5 ml) and triethylamine (7.5 ml) were added and the solvent evaporated. The residue was partitioned between ethyl acetate and saturated sodium hydrogencarbonate solution, the organics washed with brine, dried and evaporated to give a yellow oil. This oil was purified by silica gel flash column chromatography eluting with isohexane/ethyl acetate/triethylamine (99:1:0.5 through to 80:20:0.5) to afford 3-[3-(tri-n-butylstannanyl)phenyl]pyridine (11.7 g, 82%) as a colourless oil. 1H NMR (360 MHz, CDCl3) δH 0.86-0.93 (3H, m), 1.06-1.12 (2H, m), 1.28-1.40 (2H, m), 1.54-1.56 (2H, m), 7.34-7.39 (2H, m), 7.48-7.52 (2H, m), 7.62-7.65 (1H, m), 7.83-7.88 (1H, m), 8.57-8.60 (1H, m), 8.85 (1H, s).

Workup

  1. additionwas treated with
  2. customthe solvent evaporated
  3. customThe residue was partitioned between ethyl acetate and saturated sodium hydrogencarbonate solution
  4. washthe organics washed with brine
  5. customdried
  6. customevaporated
  7. customto give a yellow oil
  8. customThis oil was purified by silica gel flash column chromatography
  9. washeluting with isohexane/ethyl acetate/triethylamine (99:1:0.5 through to 80:20:0.5)

Sources & evidence

ORD record
ord-e4b038f6ba9549cca506b1b1c239e7e7
Source dataset
uspto-grants-2005_03
Patent number
US06872731B2

Reaction notes

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