Benzene → HCID 18622027, compound

HRID 1861913Notes

Reaction equation

HRID 1861913 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([CH2:10][C:11]([OH:13])=[O:12])=[CH:6][CH:5]=1)([O-:3])=[O:2].C1C=CC=CC=1.[Br:20]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(OCC)(=O)C>[Br:20][CH:10]([C:7]1[CH:6]=[CH:5][C:4]([N+:1]([O-:3])=[O:2])=[CH:9][CH:8]=1)[C:11]([OH:13])=[O:12]

Participants

6

Reactant 4

HCID 241BenzeneHCID 4661(4-Nitrophenyl)acetic acidHCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimide

Product 1

HCID 18622027HCID 18622027, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of 4-nitrophenylacetic acid (2.0 g), benzene (40 ml) and N-bromosuccinimide (3.3 g), 2,2′-azobis(2-methylpropionitrile)(0.16 g) was added and heated under reflux for 22 h. The reaction mixture was diluted with ethyl acetate and washed successively with 2 N HCl and water; the organic layer was dried with anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent, n-hexane:ethyl acetate:acetic acid=75:25:1) to give 2-bromo-2-(4-nitrophenyl)acetic acid. The resulting bromo compound was mixed with 28% aqueous ammonia solution (5 ml) and stirred at room temperature for 2 h. The reaction mixture was concentrated under reduced pressure; to the resulting residue, 1 N aqueous sodium hydroxide solution (20 ml), 1,4-dioxane (10 ml) and di-t-butyl dicarbonate (7.2 g) were added and stirred at room temperature for 2 h. The reaction mixture was concentrated under reduced pressure and the resulting residue was dissolved in a mixture of methanol (20 ml) and diethyl ether (10 ml); a solution of trimethylsilyldiazomethane (2.0 M) in n-hexane was added until the reaction mixture no longer foamed; the reaction mixture was then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent, n-hexane:ethyl acetate=3:1) to give 2-t-butoxycarbonylamino-2-(4-nitrophenyl)acetic acid methyl ester. The resulting methyl ester compound was worked up as in Example 2 to give 0.77 g of the titled compound (yield, 25%).

Workup

  1. additionwas added
  2. temperatureheated
  3. temperatureunder reflux for 22 h
  4. washwashed successively with 2 N HCl and water
  5. dry with materialthe organic layer was dried with anhydrous sodium sulfate
  6. distillationthe solvent was distilled off under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (eluent, n-hexane:ethyl acetate:acetic acid=75:25:1)

Sources & evidence

ORD record
ord-3c7f86f4c7a0439a88fe5e368f3020c4
Source dataset
uspto-grants-2003_03
Patent number
US06534546B1

Reaction notes

Loading…