Hydrochloric Acid → HCID 69275154, compound

HRID 2219196Notes

Reaction equation

HRID 2219196 reaction equation
C([O-])([O-])=O.[Na+].[Na+].[CH3:7][O:8][C:9](=[O:22])[CH2:10][O:11][C:12]1[CH:17]=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][C:13]=1Br.[C:23]1(B(O)O)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.Cl.[Na+].[Cl-]>O1CCOCC1.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.CCOC(C)=O>[CH3:7][O:8][C:9](=[O:22])[CH2:10][O:11][C:12]1[CH:17]=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][C:13]=1[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 5234Sodium ChlorideHCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 69276149HCID 69276149, compound

Product 1

HCID 69275154HCID 69275154, compoundYield 71.4%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

An aqueous Na2CO3 solution (2M, 3.79 mL) is added to a stirred solution of (2-bromo-4-nitro-phenoxy)-acetic acid methyl ester (1.06 g, 3.70 mmol), phenylboronic acid (450 mg, 3.72 mmol) and tetrakis(triphenylphosphine)palladium (0) (210 mg, 0.185 mmol) in 1,4-dioxane (10 mL) at ambient temperature under argon. The resultant mixture is heated at −95° C. for 24 hours. At ambient temperature, 5N HCl (3.8 mL) is added to the mixture, followed by the addition of EtOAc (50 mL) and saturated aqueous NaCl solution (15 mL). The organic layer is separated, dried over MgSO4, filtered and concentrated. The crude product is dissolved in MeOH (5 mL)/CH2Cl2 (20 mL) and the solution is treated dropwise with (trimethylsilyl)diazomethane (2M in hexane, 2.8 mL). After stirring for 1 hour, the mixture is concentrated and chromatographed on silica gel (gradient 50-75% CH2Cl2 in hexane) to give 760 mg (2.64 mmol, 71% yield) of the title compound as oil. ESIMS: m/z 288 (M+H)+.

Workup

  1. customThe organic layer is separated
  2. dry with materialdried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. dissolutionThe crude product is dissolved in MeOH (5 mL)/CH2Cl2 (20 mL)
  6. additionthe solution is treated dropwise with (trimethylsilyl)diazomethane (2M in hexane, 2.8 mL)
  7. concentrationthe mixture is concentrated
  8. customchromatographed on silica gel (gradient 50-75% CH2Cl2 in hexane)

Sources & evidence

ORD record
ord-f9d1d2ab3c974400b3846ff51cc3462e
Source dataset
uspto-grants-2008_08
Patent number
US07414063B2

Reaction notes

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