Dimethyl Sulfoxide → 3-Bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylbenzenamine

HRID 1638754Notes

Reaction equation

HRID 1638754 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([OH:9])=[C:4]([Br:10])[C:3]=1[CH3:11].CS(C)=O.CC(C)([O-])C.[K+].[Cl:22][C:23]1[CH:24]=[C:25]([N+:30]([O-:32])=[O:31])[CH:26]=[CH:27][C:28]=1Cl>C1(C)C=CC=CC=1>[Br:10][C:4]1[C:3]([CH3:11])=[C:2]([CH:7]=[C:6]([CH3:8])[C:5]=1[O:9][C:28]1[CH:27]=[CH:26][C:25]([N+:30]([O-:32])=[O:31])=[CH:24][C:23]=1[Cl:22])[NH2:1]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 74431,2-Dichloro-4-nitrobenzeneHCID 198414584-Amino-2-bromo-3,6-dimethylphenolHCID 23665647Potassium tert-butoxide

Product 1

HCID 198414573-Bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylbenzenamineYield 23%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Into a dry 250 milliliter round bottom flask equipped with a magnetic stirrer and nitrogen inlet was added 4-amino-2-bromo-3,6-dimethylphenol (11.94 grams, 55.3 mmol) prepared in Part B and dry dimethylsulfoxide (118 milliliters). Potassium t-butoxide (7.26 grams, 64.65 mmol) was added portionwise under nitrogen and the mixture was stirred at room temperature for 0.5 hours. Solid 3,4-dichloronitrobenzene (13.33 grams, 70.52 mmol) was then added and the reaction mixture was heated at 50° C. for 48 hours. After cooling the mixture was diluted with toluene and washed successively with saturated NH4Cl solution (3x) and with 5% NaOH solution until the aqueous washes remained colorless. This was followed by washes with water and brine, drying over Na2SO4 and solvent removal under reduced pressure to afford the crude product (9.4 grams) as a dark red-brown oil. Flash column chromatography on 650 grams of silica gel (3:1 hexane:ethyl acetate) afforded pure 3-bromo-4-(2 -chloro-4-nitrophenoxy)-2,5-dimethylaniline (4.7 grams, 12.6 mmol, 23%) as a yellow-brown solid. H'-NMR (CDCl3) 8.42 (d, J=2 Hz, 1H), 8.01 (d,d; J=2, 9 Hz; 1H), 6.55 (d, J=9 Hz, 1H), 6.58 (S, 1H), 3.73 (brS, 2H), 2.28 (S, 3H), 2.06 (S, 3H).

Workup

  1. customInto a dry 250 milliliter round bottom flask equipped with a magnetic stirrer and nitrogen inlet
  2. temperaturethe reaction mixture was heated at 50° C. for 48 hours
  3. temperatureAfter cooling the mixture
  4. washwashed successively with saturated NH4Cl solution (3x) and with 5% NaOH solution until the aqueous washes
  5. dry with materialdrying over Na2SO4 and solvent removal under reduced pressure
  6. customto afford the crude product (9.4 grams) as a dark red-brown oil

Sources & evidence

ORD record
ord-782501f4f69a47cd90c4cbffaff3f8b8
Source dataset
uspto-grants-1989_11
Patent number
US04880838

Reaction notes

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