2-Vinylpyridine → HCID 54062802, compound

HRID 1276338Notes

Reaction equation

HRID 1276338 reaction equation
Br[C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[CH:17]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=1)=[CH2:18].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C([O-])(=O)C.[Na+]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(Cl)Cl.CCCCC>[Cl:8][C:6]1[CH:5]=[CH:4][C:3]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[C:2]([CH:18]=[CH:17][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=2)[CH:7]=1

Participants

8

Reactant 4

HCID 75212-VinylpyridineHCID 80271Tri-o-tolylphosphineHCID 517045Sodium AcetateHCID 115511251-(Benzyloxy)-2-bromo-4-chlorobenzene

Product 1

HCID 54062802HCID 54062802, compoundYield 58%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 21877063Dichloromethane pentaneSolvent

Procedure

124.4 g (417.8 mmol) of 2-Bromo-4-chlorobenzyloxybenzene, 54.8 ml (501.4 mmol) of 2-vinylpyridine, 4.69 g (20.9 mmol) palladium acetate, 25.4 g (83.6 mmol) tritolylphosphine, and 48 g (584.9 mmol) sodium acetate are heated together in 200 ml DMF at 165° C. (oil bath temperature) under nitrogen for 8 hours. The cooled mixture is evaporated to dryness in vacuo. The residue is then diluted with Et2O:DCM (3:1, 1 L) and washed with sodium carbonate solution (1M, 3×1 L). The aqueous washings are extracted with Et2O:DCM (3:1, 1L) and the combined organic extract dried using MgSO4, filtered through celite, and evaporated to dryness to leave an orange solid. Flash chromatography (SiO2, DCM:pentane 3:1) gave a yellow solid which was triturated with pentane (600 ml) to give the title compound as a pale yellow solid (77.5 g, 58%), m.p. 105.2-105.8° C. 6H (250 MHz, CDCl3) 8.60 (d, J=4.5 Hz, 1H), 7.96 (d, J=16.3 Hz, 1H), 7.64-7.60 (m, 2H), 7.46-7.34 (m, 7H), 7.24 (d, J=16.6 Hz, 1H), 7.18-7.11 (m, 1H), 6.95 (d, J=8.9 Hz, 1H), 5.16 (s, 2H).

Workup

  1. customThe cooled mixture is evaporated to dryness in vacuo
  2. additionThe residue is then diluted with Et2O:DCM (3:1, 1 L)
  3. washwashed with sodium carbonate solution (1M, 3×1 L)
  4. extractionThe aqueous washings are extracted with Et2O:DCM (3:1, 1L)
  5. extractionthe combined organic extract
  6. customdried
  7. filtrationfiltered through celite
  8. customevaporated to dryness
  9. customto leave an orange solid
  10. customwas triturated with pentane (600 ml)

Sources & evidence

ORD record
ord-606a043451e840bbaf4829b273cbc08c
Source dataset
uspto-grants-2000_12
Patent number
US06166041

Reaction notes

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