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

HRID 879268Notes

Reaction equation

HRID 879268 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.[CH:20]([Sn](CCCC)(CCCC)CCCC)=[CH2:21].[Li+].[Cl-].[OH-].[Na+]>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].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

7

Reactant 4

HCID 14798Sodium HydroxideHCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 866997872-Bromo-6-methyl-4-nitrophenyl trifluoromethanesulfonate

Product 1

HCID 866997861-Bromo-3-methyl-5-nitro-2-vinylbenzeneYield 30.2%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
70 °C

Procedure

The reaction mixture of 2-Bromo-6-methyl-4-nitrophenyl trifluoromethanesulfonate (10.0 g, 27.5 mmol), vinyl-tri-n-butyltin (8.7 g, 27.5 mmol), LiCl (1.4 g, 33.0 mmol), Pd(dppf)Cl2 (673 mg, 0.92 mmol) and DMF (50 mL) was stirred at 70° C. for 3 h under N2. Then 2 N aq. NaOH (30 mL) was added and stirred at 70° C. for 10 min. The reaction mixture was cooled down, washed with saturated aqueous NaHCO3 (100 mL), and extracted with EtOAc (3×50 mL). The combined organic layer was dried over anhydrous Na2SO4, filtered, concentrated in vacuo, and purified by silica gel column (Petroleum Ether→Petroleum Ether:EtOAc (50:1)) to afford 1-Bromo-3-methyl-5-nitro-2-vinylbenzene (2.01 g, 30%) as yellow oil. 1H-NMR: 400 MHz, (CDCl3) δ: 8.29 (d, J=2.0 Hz, 1H), 8.02 (s, 1H), 6.67 (dd, J=17.6, 11.6 Hz, 1H), δ 5.75 (d, J=11.6 Hz, 1H), δ 5.49 (d, J=18.0 Hz, 1H), δ 2.48 (s, 3H).

Workup

  1. stirringstirred at 70° C. for 10 min
  2. temperatureThe reaction mixture was cooled down
  3. washwashed with saturated aqueous NaHCO3 (100 mL)
  4. extractionextracted with EtOAc (3×50 mL)
  5. dry with materialThe combined organic layer was dried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. custompurified by silica gel column (Petroleum Ether→Petroleum Ether:EtOAc (50:1))

Sources & evidence

ORD record
ord-3813509a664645ca95f99156d508bc54
Source dataset
uspto-grants-2015_03
Patent number
US08987250B2

Reaction notes

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