Tri-o-tolylphosphine → 4-ethenyl-8-nitro-3,4-dihydro-1H-isochromene

HRID 2173268Notes

Reaction equation

HRID 2173268 reaction equation
[CH2:1]([O:5][CH2:6][C:7]1[C:12]([N+:13]([O-:15])=[O:14])=[CH:11][CH:10]=[CH:9][C:8]=1Br)/[CH:2]=[CH:3]/[CH3:4].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>CC(O)=O.CC(O)=O.[Pd]>[CH:3]([CH:2]1[C:8]2[C:7](=[C:12]([N+:13]([O-:15])=[O:14])[CH:11]=[CH:10][CH:9]=2)[CH2:6][O:5][CH2:1]1)=[CH2:4]

Participants

4

Reactant 2

HCID 80271Tri-o-tolylphosphineHCID 866930082-bromo-6-nitrobenzyl (2E)-but-2-en-1-yl ether

Product 1

HCID 675178764-ethenyl-8-nitro-3,4-dihydro-1H-isochromene

Reagents, catalysts & solvents 1

HCID 4144353Palladium (II) acetateCatalyst

Procedure

To a solution of 2-bromo-6-nitrobenzyl (2E)-but-2-en-1-yl ether (3.3 g, 11.19 mmol) in TEA (100 mL) was added P(o-Tol)3 (196 mg, 0.873 mmol) and Pd(OAC)2(1.0 g, 3.21 mmol), and the mixture was stirred at reflux for 16 h. Then the mixture was concentrated in vacuo, and the mixture was partitioned between water and EtOAc. The combined organic layers were washed with HCl (1N) and brine, dried and concentrated in vacuo. The residue was purified with silica gel cloumn chromatography to give 4-ethenyl-8-nitro-3,4-dihydro-1H-isochromene. 1H-NMR (400 MHz, CDCl3) δ 7.96 (d, J=8.0 Hz, 1H), 7.45 (d, J=8.0 Hz, 1H), 7.31 (t, J=8.0 Hz, 2H), 5.74˜5.82 (m, 1H), 5.14˜5.19 (m, 2H), 5.04 (d, J=4.0 Hz, 2H), 3.93˜3.98 (m, 1H).

Workup

  1. temperatureat reflux for 16 h
  2. concentrationThen the mixture was concentrated in vacuo
  3. customthe mixture was partitioned between water and EtOAc
  4. washThe combined organic layers were washed with HCl (1N) and brine
  5. customdried
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified with silica gel cloumn chromatography

Sources & evidence

ORD record
ord-08af6d5fb5e94b3498246a1133b7bef8
Source dataset
uspto-grants-2015_06
Patent number
US09056859B2

Reaction notes

Loading…