Sodium Hydroxide → 1-Bromo-3-methyl-5-nitro-2-vinylbenzene

HRID 1468705Notes

Reaction equation

HRID 1468705 reaction equation
FC(F)(F)S(O[C:7]1[C:12]([CH3:13])=[CH:11][C:10]([N+:14]([O-:16])=[O:15])=[CH:9][C:8]=1[Br:17])(=O)=O.[CH2:20](C([Sn])=C(CCCC)CCCC)[CH2:21]CC.[Li+].[Cl-].[OH-].[Na+]>CN(C=O)C>[Br:17][C:8]1[CH:9]=[C:10]([N+:14]([O-:16])=[O:15])[CH:11]=[C:12]([CH3:13])[C:7]=1[CH:20]=[CH2:21]

Participants

6

Reactant 4

HCID 14798Sodium HydroxideHCID 433294Lithium ChlorideHCID 53438229Tri(butyl)vinyltinHCID 866997872-Bromo-6-methyl-4-nitrophenyl trifluoromethanesulfonate

Product 1

HCID 866997861-Bromo-3-methyl-5-nitro-2-vinylbenzeneYield 30%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
70 °C

Procedure

The reaction mixture of 2-bromo-6-methyl-4-nitrophenyl trifluoromethanesulfonate (65B) (10.1 g, 27.7 mmol), tributylvinyltin (8.18 ml, 27.7 mmol), LiCl (1.4 g, 33.2 mmol), PdCl2dppf (607 mg, 0.83 mmol) in DMF (50 ml) was reacted at 70° C. for 3 h. Then 2N NaOH was added and stirred at 70° C. for 5 min. The reaction mixture was cooled down, washed by sat. NaHCO3, extracted by EtOAc, dry over MgSO4, filtered, concentrated down and purified by silica gel column, eluting by 0-100% EtOAc in Hexanes to give 65C (1.9 g, 30%). 1H-NMR: 400 MHz, (CDCl3) δ: 8.30 (d, J=0.8 Hz, 1H), 8.03 (d, J=1 Hz, 1H), 6.71-6.64 (dd, J=18, 12 Hz, 1H), 5.77-5.74 (d, J=12 Hz, 1H), 5.51-5.46 (d, J=18 Hz, 1H), 2.48 (s, 3H).

Workup

  1. customwas reacted at 70° C. for 3 h
  2. temperatureThe reaction mixture was cooled down
  3. washwashed by sat. NaHCO3
  4. extractionextracted by EtOAc
  5. dry with materialdry over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated down
  8. custompurified by silica gel column
  9. washeluting by 0-100% EtOAc in Hexanes

Sources & evidence

ORD record
ord-1faa7832bde9447dbb9d270b9b89cf1e
Source dataset
uspto-grants-2015_04
Patent number
US09006229B2

Reaction notes

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