Isopropyl iodide → 2-Bromo-1-isopropoxy-3-nitrobenzene

HRID 1872876Notes

Reaction equation

HRID 1872876 reaction equation
C([O-])([O-])=O.[Cs+].[Cs+].[Br:7][C:8]1[C:13]([N+:14]([O-:16])=[O:15])=[CH:12][CH:11]=[CH:10][C:9]=1[OH:17].I[CH:19]([CH3:21])[CH3:20].CCOC(C)=O>CN(C=O)C>[Br:7][C:8]1[C:9]([O:17][CH:19]([CH3:21])[CH3:20])=[CH:10][CH:11]=[CH:12][C:13]=1[N+:14]([O-:16])=[O:15]

Participants

6

Reactant 4

HCID 6362Isopropyl iodideHCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 81672542-Bromo-3-nitrophenol

Product 1

HCID 186877232-Bromo-1-isopropoxy-3-nitrobenzeneYield 97.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

Cs2CO3 was added in 3 portions over 15 min to a stirred solution of 2-bromo-3 nitrophenol (3.00 g, 13.8 mmol) and 2-iodopropane (4.79 g, 27.6 mmol) in 50 ml anhydrous DMF cooled to 0° C. under N2. The reaction was allowed to warm to ambient temperature (2 h) and stirred overnight (17 h). EtOAc (250 ml) was added, the reaction mixture washed with water (2×250 ml) and brine (250 ml), dried (Na2SO4) and concentrated in vacuo to an orange oil (3.78 g). Purification by column chromatography (EtOAc/hexane, 5:95) afforded 3.49 g (97%) of 2-bromo-3-isopropoxynitrobenzene as a yellow oil. TLC (EtOAc/hexane 20:80)Rf =0.12; HPLC (Tr =16.1); 1H-NMR (CDCl3) d 1.35 (d, J=6 Hz, 6H), δ 4.56 (m, J=6 Hz, 1H), δ 6.95 (dd, J=8 Hz, J=3 Hz, 1H), δ 7.34 (d, J=3 Hz, 1H), δ 7.57 (d, J=8 Hz, 1H): MS m/z (relative intensity) 260 (MH+, 100), 262 (MH+ +2, 72).

Workup

  1. temperatureto warm to ambient temperature (2 h)
  2. washthe reaction mixture washed with water (2×250 ml) and brine (250 ml)
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated in vacuo to an orange oil (3.78 g)
  5. customPurification by column chromatography (EtOAc/hexane, 5:95)

Sources & evidence

ORD record
ord-ba1b8f8116cb44719ca6561b3a11fd42
Source dataset
uspto-grants-2000_08
Patent number
US06110961

Reaction notes

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