Nitrobenzene → (2,6-Dichloro-4-methoxyphenyl)(2,4-dichlorophenyl)methanone

HRID 2267215Notes

Reaction equation

HRID 2267215 reaction equation
[Al+3].[Cl-].[Cl-].[Cl-].C1([N+]([O-])=O)C=CC=CC=1.[Cl:14][C:15]1[CH:23]=[C:22]([Cl:24])[CH:21]=[CH:20][C:16]=1[C:17](Cl)=[O:18].[Cl:25][C:26]1[CH:27]=[C:28]([O:33][CH3:34])[CH:29]=[C:30]([Cl:32])[CH:31]=1>CCOCC>[Cl:25][C:26]1[CH:27]=[C:28]([O:33][CH3:34])[CH:29]=[C:30]([Cl:32])[C:31]=1[C:17]([C:16]1[CH:20]=[CH:21][C:22]([Cl:24])=[CH:23][C:15]=1[Cl:14])=[O:18]

Participants

6

Reactant 4

HCID 7416NitrobenzeneHCID 365883,5-DichloroanisoleHCID 666452,4-Dichlorobenzoyl chlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 59600765(2,6-Dichloro-4-methoxyphenyl)(2,4-dichlorophenyl)methanoneYield 85%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Anhydrous AlCl3 (4.5 g, 33.9 mmol) was placed in a round bottom flask and PhNO2 (150 mL) was added. At −78° C. 2,4-dichlorobenzoyl chloride (4.7 mL, 33.9 mmol) and 3,5-dichloro anisole (5.0 g, 28.2 mmol) were added. The reaction mixture was kept at the same temperature for 1 h and warmed to rt over 24 h. The reaction mixture was diluted with Et2O (50 mL) at 0° C. and quenched with 1N NaOH (˜30 mL). The reaction mixture was stirred vigorously until a white precipitate had been formed. The precipitates were filtered and washed with CH2Cl2 (50, 30, and 20 mL). The combined organic solvents were dried (Na2SO4), filtered, and concentrated under vacuum at ˜10 mmHg. Purification by silica gel chromatography (4:1, hexanes:CHCl3) to provide (2,6-dichloro-4-methoxyphenyl)(2,4-dichlorophenyl)methanone (8.3 g, 85%) as a white powder. 1H NMR (300 MHz, CDCl3): δ 7.68 (d, J=8.2 Hz, 1H), 7.54 (d, J=2.1 Hz, 1H), 7.37 (dd, J=8.1, 2.1 Hz, 1H), 6.95 (s, 2H), 3.87 (s, 3H); 13C NMR (75 MHz, CDCl3): δ 197.6, 163.8, 142.0, 138.3, 137.7, 136.4, 130.3, 129.9, 127.8, 122.9, 118.4, 117.9, 114.6, 56.1; IR (film): 1619 cm−1, 1584, 1553, 1400, 1309; HRMS (FAB): C14H8Cl4O2 (M+Na1) calcd. 370.91761, found 370.91765.

Workup

  1. customAt −78° C
  2. customquenched with 1N NaOH (˜30 mL)
  3. customhad been formed
  4. filtrationThe precipitates were filtered
  5. washwashed with CH2Cl2 (50, 30, and 20 mL)
  6. dry with materialThe combined organic solvents were dried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum at ˜10 mmHg
  9. customPurification by silica gel chromatography (4:1, hexanes:CHCl3)

Sources & evidence

ORD record
ord-aba60fd295e4473ead3f4c8fb23fac6b
Source dataset
uspto-grants-2010_12
Patent number
US07858825B2

Reaction notes

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