Hydrochloric Acid → HCID 69275113, compound

HRID 2219194Notes

Reaction equation

HRID 2219194 reaction equation
C([O-])([O-])=O.[Na+].[Na+].[CH3:7][O:8][C:9](=[O:20])[CH2:10][O:11][C:12]1[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][C:13]=1Br.[C:21]1(B(O)O)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=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:20])[CH2:10][O:11][C:12]1[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][C:13]=1[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 5234Sodium ChlorideHCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 43083021HCID 43083021, compound

Product 1

HCID 69275113HCID 69275113, compoundYield 26.1%

Reagents, catalysts & solvents 3

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

Procedure

An aqueous Na2CO3 solution (2M, 18.5 mL) is added to a stirred solution of (2-bromo-4-chloro-phenoxy)-acetic acid methyl ester (5.03 g, 18.0 mmol), phenylboronic acid (2.24 g, 18.4 mmol) and tetrakis(triphenylphosphine)palladium (0) (1.04 g, 0.900 mmol) in 1,4-dioxane (50 mL) at ambient temperature under argon. The resultant mixture is heated at 95° C. for 24 hours. At ambient temperature, 5N HCl (18.5 mL) is added to the mixture, followed by the addition of EtOAc (70 mL) and saturated aqueous NaCl solution (50 mL). The organic layer is separated, dried over MgSO4, filtered and concentrated. After chromatography on silica gel (CH2Cl2 followed by 0.5% HOAc/1% MeOH/98.5% CH2Cl2), 1.30 g (4.70 mmol, 26% yield) of the title compound and 2.41 g of the corresponding acid are obtained. The acid is dissolved in MeOH (5 mL)/CH2Cl2 (20 mL), and the solution is treated dropwise with (trimethylsilyl)diazomethane (2M in hexane, 8.8 mL). After stirring for 1 hour, the mixture is concentrated and chromatographed on silica gel (1:1 CH2Cl2/hexane) to give another 2.68 g of the title compound (9.68 mmol, 80% total yield) as oil. 1H NMR (CDCl3): δ3.77 (s, 3H), 4.58 (s, 2H), 6.80 (d, J=8.8 Hz, 1H), 7.21-7.26 (m, 1H), 7.33-7.37 (m, 2H), 7.42 (br t, J=7.4 Hz, 2H), 7.56 (d, J=6.9 Hz, 2H).

Workup

  1. customThe organic layer is separated
  2. dry with materialdried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-6791baa864224e68b435fdb7e7e5361b
Source dataset
uspto-grants-2008_08
Patent number
US07414063B2

Reaction notes

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