Water → 4,5-Dimethoxy-1-nitro-2-(3,3,5,5-tetramethylcyclohex-1-enyl)benzene

HRID 2218863Notes

Reaction equation

HRID 2218863 reaction equation
Br[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([O:10][CH3:11])=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13].CC1(C)C(C)(C)OB([C:23]2[CH2:28][C:27]([CH3:30])([CH3:29])[CH2:26][C:25]([CH3:32])([CH3:31])[CH:24]=2)O1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].O>COCCOC.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>[CH3:9][O:8][C:6]1[C:5]([O:10][CH3:11])=[CH:4][C:3]([N+:12]([O-:14])=[O:13])=[C:2]([C:23]2[CH2:28][C:27]([CH3:30])([CH3:29])[CH2:26][C:25]([CH3:32])([CH3:31])[CH:24]=2)[CH:7]=1

Participants

8

Reactant 4

HCID 962Water2×HCID 62657Potassium Phosphate, TribasicHCID 1709684-Bromo-5-nitroveratroleHCID 231420594,4,5,5-Tetramethyl-2-(3,3,5,5-tetramethylcyclohex-1-en-1-yl)-1,3,2-dioxaborolane

Product 1

HCID 231419224,5-Dimethoxy-1-nitro-2-(3,3,5,5-tetramethylcyclohex-1-enyl)benzeneYield 85.2%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 1-bromo-4,5-dimethoxy-2-nitrobenzene (1.06 g, 4.04 mmol) produced in Example (87a) in 1,2-dimethoxyethane (30 mL) were added 4,4,5,5-tetramethyl-2-(3,3,5,5-tetramethylcyclohex-1-enyl)[1,3,2]dioxaborolane (1.28 g, 4.85 mmol) produced in Example (4b), tripotassium phosphate (1.29 g, 6.06 mmol) and water (1.5 mL). Tetrakis(triphenylphosphine)palladium (230 mg, 0.20 mmol) was then added to the mixture while stirring at room temperature under a nitrogen atmosphere. The mixture was then stirred for 13 hours at an external temperature of 70° C., and stirring was continued for 3 hours at an external temperature of 100° C. Tetrakis(triphenylphosphine)palladium(0) (230 mg, 0.20 mmol) and water (2 mL) were added to the reaction mixture, and it was further stirred for 9 hours at an external temperature of 100° C. and then for 11 hours at an external temperature of 70° C. After cooling the reaction mixture, ethyl acetate was added and the mixture was filtered through Celite. The filtrate was concentrated and extracted with ethyl acetate, and the obtained organic layer was washed with brine. The organic layer was then dried over anhydrous magnesium 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/heptane) to give 1.1 g of the title compound as a brown oil.

Workup

  1. stirringThe mixture was then stirred for 13 hours at an external temperature of 70° C.
  2. stirringstirring
  3. stirringwas further stirred for 9 hours at an external temperature of 100° C.
  4. waitfor 11 hours at an external temperature of 70° C
  5. additionwas added
  6. filtrationthe mixture was filtered through Celite
  7. concentrationThe filtrate was concentrated
  8. extractionextracted with ethyl acetate
  9. washthe obtained organic layer was washed with brine
  10. dry with materialThe organic layer was then dried over anhydrous magnesium sulfate
  11. filtrationthe desiccant was filtered off
  12. concentrationthe filtrate was concentrated under reduced pressure
  13. customThe resultant residue was purified by silica gel column chromatography (ethyl acetate/heptane)

Sources & evidence

ORD record
ord-1e08fb8ea73d4f05ba0259b780e7a4a6
Source dataset
uspto-grants-2008_08
Patent number
US07410971B2

Reaction notes

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