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

HRID 1474231Notes

Reaction equation

HRID 1474231 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 silica 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 silica 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-8fec96d151aa4d13921b334ebd71c535
Source dataset
uspto-grants-2015_04
Patent number
US09018211B2

Reaction notes

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