Water → HCID 58368582, compound

HRID 1192513Notes

Reaction equation

HRID 1192513 reaction equation
[Cl:1][C:2]1[C:3]([C:23]#[C:24][Si:25]([CH3:28])([CH3:27])[CH3:26])=[C:4]([N+:20]([O-:22])=[O:21])[C:5](OS(C(F)(F)F)(=O)=O)=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[F:29][C:30]1[CH:31]=[C:32](B(O)O)[CH:33]=[CH:34][CH:35]=1.O.C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.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>[Cl:1][C:2]1[CH:11]=[C:6]([C:7]([O:9][CH3:10])=[O:8])[C:5]([C:34]2[CH:33]=[CH:32][CH:31]=[C:30]([F:29])[CH:35]=2)=[C:4]([N+:20]([O-:22])=[O:21])[C:3]=1[C:23]#[C:24][Si:25]([CH3:26])([CH3:27])[CH3:28]

Participants

7

Reactant 4

HCID 962WaterHCID 516892Sodium BicarbonateHCID 27339863-Fluorophenylboronic acidHCID 58368634HCID 58368634, compound

Product 1

HCID 58368582HCID 58368582, compoundYield 87.5%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of methyl 5-chloro-3-nitro-2-{[(trifluoromethyl)sulfonyl]oxy}-4-[(trimethylsilyl)ethynyl]benzoate (9.3 g, 20 mmol) and (3-fluorophenyl)boronic acid (4.3 g, 30 mmol) in toluene (200 mL) was treated with water (200 mL) saturated with sodium bicarbonate (3.4 g, 40 mmol). The reaction mixture was degassed with nitrogen for 10 minutes, treated with tetrakis(triphenylphosphine)palladium(0) (1.2 g, 1.0 mmol), degassed with nitrogen for 10 minutes, and heated at 80° C. for 6 hours. The reaction mixture was cooled to 20° C. and the organic layer was separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were dried with sodium sulfate, filtered, and concentrated to a crude residue. The crude material was diluted with dichloromethane and adsorbed onto 36 g of silica gel. Purification by flash column chromatography using ethyl acetate in hexanes (0%-40%) gave the desired product (7.1 g, 86%). LCMS for C19H18ClFNO4Si (M+H)+: m/z=406.1; Found: 405.7.

Workup

  1. customThe reaction mixture was degassed with nitrogen for 10 minutes
  2. customdegassed with nitrogen for 10 minutes
  3. temperatureThe reaction mixture was cooled to 20° C.
  4. customthe organic layer was separated
  5. extractionThe aqueous layer was extracted with ethyl acetate
  6. dry with materialThe combined organic layers were dried with sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated to a crude residue
  9. additionThe crude material was diluted with dichloromethane
  10. customPurification by flash column chromatography

Sources & evidence

ORD record
ord-8068b3b751d24284ae61b1a7e3b2db43
Source dataset
uspto-grants-2014_03
Patent number
US08680108B2

Reaction notes

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