Dimethylformamide → 5-Methoxy-2-naphthonitrile

HRID 890948Notes

Reaction equation

HRID 890948 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[CH:12][C:13]=2[O:17][CH3:18])[CH:8]=1)(=O)=O.[CH3:21][N:22](C=O)C>[C-]#N.[Zn+2].[C-]#N.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>[CH3:18][O:17][C:13]1[CH:12]=[CH:11][CH:10]=[C:9]2[C:14]=1[CH:15]=[CH:16][C:7]([C:21]#[N:22])=[CH:8]2

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 222433875-Methoxy-2-naphthyl trifluoromethanesulfonate

Product 1

HCID 222435175-Methoxy-2-naphthonitrileYield 90%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
80 °C

Procedure

A solution of 5-methoxy-2-naphthyl trifluoromethanesulfonate (1.04 g, 3.4 mmol) in DMF (5 mL) is degassed by repeatedly evacuating the flask then flushing with N2. Zinc cyanide (234 mg, 2.0 mmol) is added followed by Pd(PPh3)4 (196 mg, 0.17 mmol). The resulting mixture is again degassed and heated to 80° C. for 3 hours. The reaction is allowed to cool, poured into water and washed twice with toluene and once with CH2Cl2. The combined organic extracts are dried (Na2SO4), filtered and concentrated. The resulting material is purified by column chromatography (step gradient, 25–50% CH2Cl2 in hexanes) to give 5-methoxy-2-naphthonitrile as a white solid (560 mg, 90%). HRMS (EI) calculated for C12H9NO 183.0684, found 183.0684.

Workup

  1. customby repeatedly evacuating the flask
  2. customthen flushing with N2
  3. customThe resulting mixture is again degassed
  4. temperatureto cool
  5. additionpoured into water
  6. washwashed twice with toluene and once with CH2Cl2
  7. dry with materialThe combined organic extracts are dried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe resulting material is purified by column chromatography (step gradient, 25–50% CH2Cl2 in hexanes)

Sources & evidence

ORD record
ord-9a887f0069344a16bab6c1bb50451e9a
Source dataset
uspto-grants-2006_02
Patent number
US07001900B2

Reaction notes

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