3,4-Dimethoxybenzonitrile → HCID 4711749, compound

HRID 2301940Notes

Reaction equation

HRID 2301940 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:10]=1[O:11][CH3:12])[C:6]#[N:7].[C:13]1([Mg]Br)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(OCC)(=O)C.C(Cl)Cl.[BH4-].[Na+]>O1CCCC1.CO>[C:13]1([CH:6]([NH2:7])[C:5]2[CH:8]=[CH:9][C:10]([O:11][CH3:12])=[C:3]([O:2][CH3:1])[CH:4]=2)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 748423,4-DimethoxybenzonitrileHCID 4311764Sodium borohydrideHCID 21226138Dichloromethane ethylacetateHCID 178418255HCID 178418255, compound

Product 1

HCID 4711749HCID 4711749, compoundYield 72.3%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirring solution of 3,4-dimethoxybenzonitrile (1.63 grams, 10.0 mmol) in tetrahydrofuran (25 milliliters) was added phenyl magnesium bromide (3.7 milliliters, 3M, 11.0 mmol) and the resulting solution was refluxed for 40 minutes. The progress of the reaction was monitored by TLC (30% ethyl acetate/methylene chloride, UV), after 40 minutes the reaction was complete. The reaction mixture was allowed to cool and methanol (25 milliliters) was added slowly. When the effervescence had ceased sodium borohydride (0.40 grams, 10.5 mmol) was added slowly and the reaction mixture was stirred at room temperature overnight. The resulting dark purple mixture was extracted with ether (3 times with 50 milliliters) and the combined ether extracts back extracted into aqueous 3N hydrochloric acid (150 milliliters). The pH of the aqueous layer was then adjusted to 14 using sodium hydroxide (5 Molar) and the mixture was extracted with methylene chloride (2 times with 50 milliliters). The combined organic layers were dried over magnesium sulfate and concentrated in vacuo to afford 1.76 grams (72%) of product as an orange oil: 1H NMR (CDCl3) δ7.43-7.16(m, 5H), 6.95-6.74(m, 3H), 5.17(s, 1H), 3.85(s, 3H), 3.84(s, 3H), 1.78(s, 2H).

Workup

  1. temperaturethe resulting solution was refluxed for 40 minutes
  2. temperatureto cool
  3. additionwas added slowly
  4. extractionThe resulting dark purple mixture was extracted with ether (3 times with 50 milliliters)
  5. extractionthe combined ether extracts back extracted into aqueous 3N hydrochloric acid (150 milliliters)
  6. extractionthe mixture was extracted with methylene chloride (2 times with 50 milliliters)
  7. dry with materialThe combined organic layers were dried over magnesium sulfate
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d800ffa998e445a591badf4f9f16403f
Source dataset
uspto-grants-2002_08
Patent number
US06429221B1

Reaction notes

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