Dimethyl Sulfate → HCID 86659132, compound

HRID 2365749Notes

Reaction equation

HRID 2365749 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH2:10][C:11]([CH:13]([C:16]#[N:17])[C:14]#[N:15])=[O:12])[CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2].[C:18]([O-])(O)=O.[Na+].S(OC)(OC)(=O)=O>O.O1CCOCC1.CCOC(C)=O.[Cl-].[Na+].O>[CH3:18][O:12][C:11](=[C:13]([C:16]#[N:17])[C:14]#[N:15])[CH2:10][C:6]1[CH:7]=[CH:8][CH:9]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1

Participants

8

Reactant 3

HCID 6497Dimethyl SulfateHCID 516892Sodium BicarbonateHCID 86659133HCID 86659133, compound

Product 1

HCID 86659132HCID 86659132, compound

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
80 °C

Procedure

The crude material containing 2-(2-(3-nitrophenyl)acetyl)malononitrile was dissolved in H2O (7 mL) and 1,4-dioxane (42 mL), to which NaHCO3 (11.5 g, 138 mmol) and dimethyl sulfate (10.5 mL, 110 mmol) were added. The reaction mixture was heated to 80° C. and left stirring for 12 hours. The reaction mixture was diluted with EtOAc (100 mL) and brine (100 mL). The aqueous portion was extracted with EtOAc (3×100 mL). The combined organic fractions were dried over MgSO4, filtered, and concentrated in vacuo. The recovered solid was purified by silica gel chromatography (100% chloroform). Fractions containing the desired enol ether were pooled, concentrated, and dissolved in hot MeOH. The solution was cooled and fine white crystals formed overnight, which were recovered by filtration and washed with ice cold MeOH to afford 2-(1-methoxy-2-(3-nitrophenyl)ethylidene)malononitrile. 1H NMR (400 MHz, DMSO): δ 7.78 (1H, d), 7.72 (t, 1H), 8.22 (d, 1H), 8.25 (s, 1H), 4.36 (s, 2H), 4.04 (s, 3H).

Workup

  1. waitleft
  2. extractionThe aqueous portion was extracted with EtOAc (3×100 mL)
  3. dry with materialThe combined organic fractions were dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe recovered solid was purified by silica gel chromatography (100% chloroform)
  7. additionFractions containing the desired enol ether
  8. concentrationconcentrated
  9. dissolutiondissolved in hot MeOH
  10. temperatureThe solution was cooled
  11. customfine white crystals formed overnight
  12. filtrationwhich were recovered by filtration
  13. washwashed with ice cold MeOH

Sources & evidence

ORD record
ord-8a341df17e594a418f0703229b826e23
Source dataset
uspto-grants-2014_04
Patent number
US08697709B2

Reaction notes

Loading…