Water → 2-bromo-N-(2-methyl-2-propenyl)-5-nitroaniline

HRID 2294484Notes

Reaction equation

HRID 2294484 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][C:5]=1[NH2:6].Br[CH2:15][C:16]([CH3:18])=[CH2:17].O>C1COCC1>[Br:3][C:4]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][C:5]=1[NH:6][CH2:17][C:16]([CH3:18])=[CH2:15]

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 826072-Bromo-5-nitroanilineHCID 3577853-Bromo-2-methyl-1-propene

Product 1

HCID 234335482-bromo-N-(2-methyl-2-propenyl)-5-nitroanilineYield 32.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of NaH 60% dispersion in oil (97 mg, 0.0023 mol) in 2 mL of anhydrous THF at 0° C. was added 2-bromo-5-nitroaniline (500 mg, 0.0023 mol) in 2 mL of THF dropwise, the temperature was raised to rt to complete deprotonation then lowered to 0° C. 3-bromo-2-methylpropene (232 mL, 0.0023 mol) was added very slowly and the reaction mixture was stirred at 0° C. for 3 h then neutralized with water (5 mL). The mixture was extracted with ethyl acetate (2×10 mL), dried (Na2SO4) and concentrated in vacuo to an oil that was subjected to flash column chromatography (silica gel, hexanes/ethyl acetate, 8:2) to give 200 mg (32%) of 2-bromo-N-(2-methyl-2-propenyl)-5-nitroaniline (structure 55A of Scheme XLVII, where R1 =methyl, R2 =H). Data for 2-bromo-N-(2-methyl-2-propenyl)-5-nitroaniline: 1H NMR (400 MHz, CDCl3) 7.55 (d, J=8.5, 1H), 7.40 (dd, J=8.5, 2.8, 1H), 7.39 (d, J=2.8, 1H), 4.96 (s, 2H), 4.95 (bs, 1H), 3.82 (d, J=5.9, 2H), 1.81 (s, 3H).

Workup

  1. customthen lowered to 0° C
  2. extractionThe mixture was extracted with ethyl acetate (2×10 mL)
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated in vacuo to an oil that

Sources & evidence

ORD record
ord-c9863e0ec04f4f0e81a61532de9aa74f
Source dataset
uspto-grants-1997_11
Patent number
US05688810

Reaction notes

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