Toluene → 1-Fluoro-3-nitro-2-(3,3,5,5-tetramethylcyclohex-1-enyl)benzene

HRID 2218879Notes

Reaction equation

HRID 2218879 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[C:3]=1OS(C(F)(F)F)(=O)=O.CC1(C)C(C)(C)OB([C:27]2[CH2:32][C:31]([CH3:34])([CH3:33])[CH2:30][C:29]([CH3:36])([CH3:35])[CH:28]=2)O1.C1(C)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(OCC)(=O)C.O.C(O)C>[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[C:3]=1[C:27]1[CH2:32][C:31]([CH3:34])([CH3:33])[CH2:30][C:29]([CH3:36])([CH3:35])[CH:28]=1

Participants

9

Reactant 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 200290852-Fluoro-6-nitrophenyl TrifluoromethanesulfonateHCID 231420594,4,5,5-Tetramethyl-2-(3,3,5,5-tetramethylcyclohex-1-en-1-yl)-1,3,2-dioxaborolane

Product 1

HCID 231415691-Fluoro-3-nitro-2-(3,3,5,5-tetramethylcyclohex-1-enyl)benzeneYield 81.1%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
100 °C

Procedure

To a mixture of trifluoromethanesulfonic acid 2-fluoro-6-nitrophenyl ester (2.89 g, 10 mmol) produced in Example (97a), 4,4,5,5-tetramethyl-2-(3,3,5,5-tetramethylcyclohex-1-enyl)[1,3,2]dioxaborolane (3.17 g, 12 mmol) produced in Example (4b), toluene (30 mL) and ethanol (15 mL) were added sodium carbonate (1.6 g, 15.1 mmol), purified water (0.9 mL) and tetrakis(triphenylphosphine)palladium(0) (1.15 g, 1 mmol), followed by stirring for 2 hours at an external temperature of 100° C. under a nitrogen atmosphere. Ethyl acetate and water were added to the reaction mixture and extraction was performed with ethyl acetate. The separated organic layer was washed with brine and then dried over anhydrous sodium sulfate. The desiccant was filtered off and the filtrate was concentrated under reduced pressure. The resultant residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give 2.25 g of the title compound as a light yellow oil.

Workup

  1. washThe separated organic layer was washed with brine
  2. dry with materialdried over anhydrous sodium sulfate
  3. filtrationThe desiccant was filtered off
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customThe resultant residue was purified by silica gel column chromatography (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-9fb074eea30a4879b89504028b06b949
Source dataset
uspto-grants-2008_08
Patent number
US07410971B2

Reaction notes

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