Water → Methyl 4-(2-cyano-3-ethylphenoxy)-3-methylbenzoate

HRID 1500979Notes

Reaction equation

HRID 1500979 reaction equation
Br[C:2]1[C:19]([CH2:20][CH3:21])=[CH:18][CH:17]=[CH:16][C:3]=1[O:4][C:5]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[CH:7][C:6]=1[CH3:15].O.[CH3:23][N:24](C)C=O>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C-]#N.[Zn+2].[C-]#N>[C:23]([C:2]1[C:19]([CH2:20][CH3:21])=[CH:18][CH:17]=[CH:16][C:3]=1[O:4][C:5]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[CH:7][C:6]=1[CH3:15])#[N:24]

Participants

6

Reactant 3

HCID 962WaterHCID 6228DimethylformamideHCID 89580615HCID 89580615, compound

Product 1

HCID 89580995Methyl 4-(2-cyano-3-ethylphenoxy)-3-methylbenzoateYield 61%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst

Conditions

Temperature
140 °C

Procedure

To a solution of methyl 4-(2-bromo-3-ethylphenoxy)-3-methylbenzoate (1.0 g, 2.9 mmol) in N,N-dimethylformamide was added tetrakis(triphenylphosphine) palladium(0) (0.35 g, 0.3 mmol) and zinc cyanide (1.2 g, 10 mmol). The reaction mixture was stirred at 140° C. for 12 hours. After the reaction, the mixture was poured into water (50 mL) and the solution was extracted with ethyl acetate (50 mL). The organic phase was dried over anhydrous sodium sulfate. The mixture was filtered and the filtrate was concentrated. The residue was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=20:1) to give the pure product methyl 4-(2-cyano-3-ethylphenoxy)-3-methylbenzoate as a colorless oil (0.52 g, 61%). 1H NMR (300 MHz, CDCl3): δ 7.99 (d, J=1.8 Hz, 1H), 7.89 (dd, J=8.4 Hz, J=2.1 Hz, 1H), 7.55 (d, J=8.7 Hz, 1H), 6.95 (d, J=8.4 Hz, 1H), 6.86 (d, J=2.4 Hz, 1H), 6.76 (dd, J=8.4 Hz, J=2.4 Hz, 1H), 3.92 (s, 3H), 2.83 (q, J=7.5 Hz, 2H), 2.26 (s, 3H), 1.27 (t, J=7.5 Hz, 3H).

Workup

  1. customAfter the reaction
  2. extractionthe solution was extracted with ethyl acetate (50 mL)
  3. dry with materialThe organic phase was dried over anhydrous sodium sulfate
  4. filtrationThe mixture was filtered
  5. concentrationthe filtrate was concentrated
  6. customThe residue was purified by column chromatography (silica gel, petroleum ether/ethyl acetate=20:1)

Sources & evidence

ORD record
ord-22795a0359cf46418ae9bdef6e7d62c5
Source dataset
uspto-grants-2015_12
Patent number
US09206128B2

Reaction notes

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