1-Propanol → 2-Ethoxy-1-nitro-4-vinylbenzene

HRID 419495Notes

Reaction equation

HRID 419495 reaction equation
[CH2:1]([O:3][C:4]1[CH:9]=[C:8](Br)[CH:7]=[CH:6][C:5]=1[N+:11]([O-:13])=[O:12])[CH3:2].[CH2:14](O)[CH2:15]C>C(Cl)Cl.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:1]([O:3][C:4]1[CH:9]=[C:8]([CH:14]=[CH2:15])[CH:7]=[CH:6][C:5]=1[N+:11]([O-:13])=[O:12])[CH3:2]

Participants

5

Reactant 2

HCID 10311-PropanolHCID 155555014-Bromo-2-ethoxy-1-nitrobenzene

Product 1

HCID 594527892-Ethoxy-1-nitro-4-vinylbenzeneYield 81%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
100 °C

Procedure

To 5-bromo-2-nitrophenyl ethyl ether (8.8 g, 35.76 mmol) in 80 mL of n-propanol was added, PdCl2(dppf)*DCM (0.523 g, 0.72 mmol), potassium ethenyl(trifluoro)borate (6.71 g, 50 mmol), and TEA (3.61 g, 35.76 mmol). The mixture was heated to 100° C. for 3 h. The solvent was rotovaped down and the residue dissolved in DCM, and filtered to remove insoluble solids. 20 g of silica gel was added and the solvent rotovaped down, and purified by flash chromatography to give the title compound of step B (5.58 g, 28.89 mmol, 81%) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.81 (d, J=8.97 Hz, 1H), 7.01-7.03 (m, 1H), 6.68 (dd, J=17.67, 10.71 Hz, 1H), 5.84 (d, J=17.58 Hz, 1H), 5.44 (d, J=11.17 Hz, 1H), 4.19 (q, J=6.96 Hz, 2H), 1.47 (t, J=6.96 Hz, 3H).

Workup

  1. filtrationfiltered
  2. customto remove insoluble solids
  3. addition20 g of silica gel was added
  4. custompurified by flash chromatography

Sources & evidence

ORD record
ord-e47086b2437c4d7a9e67b7d461283781
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Reaction notes

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