Ethyl Acetate → 2-(Methyloxy)-4-prop-2-en-1-ylbenzonitrile

HRID 1186972Notes

Reaction equation

HRID 1186972 reaction equation
[CH3:1][O:2][C:3]1[CH:10]=[C:9](Br)[CH:8]=[CH:7][C:4]=1[C:5]#[N:6].[CH2:12]([Sn](CCCC)(CCCC)CCCC)[CH:13]=[CH2:14].[Cl-].[Li+].CCOC(C)=O>C1(C)C=CC=CC=1.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>[CH3:1][O:2][C:3]1[CH:10]=[C:9]([CH2:14][CH:13]=[CH2:12])[CH:8]=[CH:7][C:4]=1[C:5]#[N:6]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 90628AllyltributylstannaneHCID 433294Lithium ChlorideHCID 223467024-Bromo-2-methoxybenzonitrile

Product 1

HCID 666438682-(Methyloxy)-4-prop-2-en-1-ylbenzonitrile

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
130 °C

Procedure

To a 50 mL flask containing a stir bar were added 2-methoxy-4-bromobenzonitrile (0.30 g, 1.4 mmol), palladium tetrakis (82 mg, 0.071 mmol), allyltri-n-butyltin (0.877 mL, 2.83 mmol), and lithium chloride (0.120 g, 2.83 mmol). The resulting mixture was then dissolved in anhydrous toluene (16 mL); the flask was placed in an oil bath and heated at 130° C.; LC as well as TLC (hexanes/EtOAc=1/0.3) indicated that reaction had gone to completion. The flask was taken out of the oil bath and cooled to room temperature. To the flask was poured EtOAc (40 mL) and the mixture was transferred into a separatory funnel and washed with aqueous NaCl. The organic phase was dried over Na2SO4, filtered and concentrated to dryness. It was then dissolved in DCM and absorbed into silica gel. The slica gel was then loaded onto a silica column for separation with the solvent systems of hexanes/EtOAc (1/0.3); this gave 2-(methyloxy)-4-prop-2-en-1-ylbenzonitrile. LC-MS (IE, m/z): 174 [M+1]+; tR=2.10 min.

Workup

  1. additionTo a 50 mL flask containing a stir bar
  2. customthe flask was placed in an oil bath
  3. temperaturecooled to room temperature
  4. customthe mixture was transferred into a separatory funnel
  5. washwashed with aqueous NaCl
  6. dry with materialThe organic phase was dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated to dryness
  9. dissolutionIt was then dissolved in DCM
  10. customabsorbed into silica gel
  11. customThe slica gel was then loaded onto a silica column for separation with the solvent systems of hexanes/EtOAc (1/0.3)

Sources & evidence

ORD record
ord-1755956e42b14cb0a520f8cc0a8e679c
Source dataset
uspto-grants-2014_03
Patent number
US08673920B2

Reaction notes

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