Methyl 2-chloro-4-nitrobenzoate → Methyl 2-cyano-4-nitrobenzoate

HRID 2202378Notes

Reaction equation

HRID 2202378 reaction equation
Cl[C:2]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[C:15]([Cu])#[N:16]>CN(C=O)C.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:15]([C:2]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])#[N:16]

Participants

5

Reactant 2

HCID 83343Methyl 2-chloro-4-nitrobenzoateHCID 178418546HCID 178418546, compound

Product 1

HCID 10104417Methyl 2-cyano-4-nitrobenzoateYield 46.9%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Procedure

A mixture of methyl 2-chloro-4-nitrobenzoate (2 g, 9.3 mmol), CuCN (3.3 g, 37.2 mmol), and Pd(PPh3)4 (1.075 g, 0.93 mmol) was suspended in DMF (15 mL) and then subjected to microwave irradiation at 150° C. for 4 hours. After the mixture was concentrated under reduced pressure, the residue was partitioned between ethyl acetate and water. The organic layer was dried over Na2SO4, filtered, and the filtrate was evaporated to dryness under reduced pressure. The crude material was purified by column chromatography (20% EA/PE) to afford 0.9 g of title compound. LC-MS: m/z 207.1 (M+H)+.

Workup

  1. customirradiation at 150° C. for 4 hours
  2. concentrationAfter the mixture was concentrated under reduced pressure
  3. customthe residue was partitioned between ethyl acetate and water
  4. dry with materialThe organic layer was dried over Na2SO4
  5. filtrationfiltered
  6. customthe filtrate was evaporated to dryness under reduced pressure
  7. customThe crude material was purified by column chromatography (20% EA/PE)

Sources & evidence

ORD record
ord-edd8dda3b8f64c4286fe7154488833c3
Source dataset
uspto-grants-2016_06
Patent number
US09365545B2

Reaction notes

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