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

HRID 32219

反応式

HRID 32219 の反応式
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

参加物

8

反応物 4

HCID 962Water2 回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

生成物 1

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

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒2 回HCID 80711,2-Dimethoxyethane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-1dfb7b5957634bf6b1e95578f2f86a12
出典データセット
uspto-grants-2008_09
特許番号
US07425554B2

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