Dimethylformamide → Methyl (2-chloro-4-cyano-5-methoxyphenyl)acetate

HRID 2173339Notes

Reaction equation

HRID 2173339 reaction equation
[CH3:1][O:2][C:3](=[O:22])[CH2:4][C:5]1[CH:10]=[C:9]([O:11][CH3:12])[C:8](OS(C(F)(F)F)(=O)=O)=[CH:7][C:6]=1[Cl:21].[CH3:23][N:24](C=O)C>[Cl-].[Na+].O.[C-]#N.[C-]#N.[Zn+2].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:21][C:6]1[CH:7]=[C:8]([C:23]#[N:24])[C:9]([O:11][CH3:12])=[CH:10][C:5]=1[CH2:4][C:3]([O:2][CH3:1])=[O:22]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 1254976274-((Methoxycarbonyl)methyl)-5-chloro-2-methoxyphenyl trifluoromethanesulfonate

Product 1

HCID 77231255Methyl (2-chloro-4-cyano-5-methoxyphenyl)acetate

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 57417360Sodium chloride; waterSolvent

Procedure

A mixture of methyl(2-chloro-5-methoxy-4-{[(trifluoromethyl)sulfonyl]oxy}phenyl)acetate (200 mg, 0.551 mmol), Zn(CN)2 (39 mg, 0.331 mmol) and Pd(PPh3)4 (50 mg, 0.043 mmol) in 10 mL of DMF was heated at 110˜120° C. under N2 overnight. Cooled to ambient temperature and the mixture was poured into brine (50 mL) and extracted with EtOAc (3*50 mL). The combined organic layers were washed with water (50 mL), brine (50 mL), dried over anhydrous Na2SO4 and concentrated. The residue was purified by prep-TLC to give methyl (2-chloro-4-cyano-5-methoxyphenyl)acetate.

Workup

  1. temperaturewas heated at 110˜120° C. under N2 overnight
  2. extractionextracted with EtOAc (3*50 mL)
  3. washThe combined organic layers were washed with water (50 mL), brine (50 mL)
  4. dry with materialdried over anhydrous Na2SO4
  5. concentrationconcentrated
  6. customThe residue was purified by prep-TLC

Sources & evidence

ORD record
ord-9f33b3e3330b400683c28bc5420d44b9
Source dataset
uspto-grants-2015_06
Patent number
US09056859B2

Reaction notes

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