2-Bromo-1,3-difluoro-4-nitrobenzene → 1,3-Difluoro-4-nitro-2-vinylbenzene

HRID 243198Notes

Reaction equation

HRID 243198 reaction equation
Br[C:2]1[C:7]([F:8])=[C:6]([N+:9]([O-:11])=[O:10])[CH:5]=[CH:4][C:3]=1[F:12].[CH2:13](C([SnH3])=C(CCCC)CCCC)[CH2:14]CC>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:12][C:3]1[CH:4]=[CH:5][C:6]([N+:9]([O-:11])=[O:10])=[C:7]([F:8])[C:2]=1[CH:13]=[CH2:14]

Participants

5

Reactant 2

HCID 137327452-Bromo-1,3-difluoro-4-nitrobenzeneHCID 21115800Tri(butyl)vinylstannane

Product 1

HCID 681573311,3-Difluoro-4-nitro-2-vinylbenzeneYield 77%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

A solution of 2-bromo-1,3-difluoro-4-nitrobenzene (0.20 g, 0.84 mmol), tributylvinylstannane (0.27 mL, 0.924 mmol) and Pd(PPh3)4 (48.6 mg, 0.042 mmol) in dioxane (4 mL) was heated at 150° C. for 1 h using microwave irradiation. The cooled reaction mixture was concentrated in vacuo, the resulting residue was purified by column chromatography (Si—PCC, eluant 2-10% EtOAc in cyclohexane) affording the title compound as a pale orange oil (0.119 g, 77%). 1H NMR (CDCl3, 300 MHz): 8.01-7.93 (1H, m), 7.03 (1H, dt, J=9.2, 1.9 Hz), 6.71 (1H, dd, J=18.0, 12.0 Hz), 6.15 (1H, d, J=18.0 Hz), 5.77 (1H, d, J=12.0 Hz)

Workup

  1. custommicrowave irradiation
  2. customThe cooled reaction mixture
  3. concentrationwas concentrated in vacuo
  4. customthe resulting residue was purified by column chromatography (Si—PCC, eluant 2-10% EtOAc in cyclohexane)

Sources & evidence

ORD record
ord-54ac3236bc1b49c0853c14f291462536
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

Loading…