2-Methylbenzenesulfonic acid → 8-[3-Bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylphenyl]-8-azabicyclo[4.3.0]-nonan-7,9-dione

HRID 1638755Notes

Reaction equation

HRID 1638755 reaction equation
[Br:1][C:2]1[C:3]([CH3:21])=[C:4]([CH:6]=[C:7]([CH3:20])[C:8]=1[O:9][C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][C:11]=1[Cl:19])[NH2:5].[C@@H:22]12[C:31](=O)[O:30][C:28](=[O:29])[C@@H:23]1[CH2:24][CH2:25][CH2:26][CH2:27]2.C1(C)C(S(O)(=O)=O)=CC=CC=1>C1(C)C=CC=CC=1>[Br:1][C:2]1[C:3]([CH3:21])=[C:4]([N:5]2[C:28](=[O:29])[CH:23]3[CH:22]([CH2:27][CH2:26][CH2:25][CH2:24]3)[C:31]2=[O:30])[CH:6]=[C:7]([CH3:20])[C:8]=1[O:9][C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][C:11]=1[Cl:19]

Participants

5

Reactant 3

HCID 69252-Methylbenzenesulfonic acidHCID 641660Hexahydrophthalic anhydride, cis-HCID 198414573-Bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylbenzenamine

Product 1

HCID 198414688-[3-Bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylphenyl]-8-azabicyclo[4.3.0]-nonan-7,9-dioneYield 84.5%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 3-bromo-4-(2-chloro-4-nitrophenoxy)-2,5-dimethylaniline (4.7 grams, 12.65 mmol) prepared in Part C in toluene (40 milliliters) was added cis-1,2-cyclohexane dicarboxylic anhydride (20.48 grams, 132.83 mmol) and a spatula tipful of toluene sulfonic acid. The reaction mixture was heated at reflux overnight and allowed to cool; washed with 5% NaOH solution (5x), water (3x) and brine (1x); dried over Na2SO4 and concentrated under reduced pressure to afford the crude desired product as a thick brown oil (5.43 grams, 10.69 mmol, 84%) which crystallized on standing and had a melting point of 187° C.-190° C. H'-NMR (CDCl3) 8.40 (d, J=2 Hz, 1H), 8.02 (d,d; J=2, 9 Hz, 1H), 7.00 (br, 5, 1H), 6.55 (d, J=9 Hz, 1H), 3.10 (M, 2H), 2.21 (brS, 6H), 1.93 (M, 4H), 1.58 (m, 4H).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux overnight
  3. temperatureto cool
  4. washwashed with 5% NaOH solution (5x), water (3x) and brine (1x)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-cceddabcfc5d4b9f8fc2afccc6f454c5
Source dataset
uspto-grants-1989_11
Patent number
US04880838

Reaction notes

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