Dimethyl Sulfate → 2-((3-Ethoxy-4-methoxyphenyl)(methoxy)methylene)malononitrile

HRID 238062Notes

Reaction equation

[CH2:1]([O:3][C:4]1[CH:5]=[C:6]([C:12]([OH:18])=[C:13]([C:16]#[N:17])[C:14]#[N:15])[CH:7]=[CH:8][C:9]=1[O:10][CH3:11])[CH3:2].[C:19](=O)(O)[O-].[Na+].O1CCOCC1.COS(OC)(=O)=O>O>[CH2:1]([O:3][C:4]1[CH:5]=[C:6]([C:12]([O:18][CH3:19])=[C:13]([C:14]#[N:15])[C:16]#[N:17])[CH:7]=[CH:8][C:9]=1[O:10][CH3:11])[CH3:2]

Participants

Conditions

Temperature: 85 °C

Procedure

2-((3-ethoxy-4-methoxyphenyl)(hydroxy)methylene)malononitrile (25.5 mmol) and sodium bicarbonate (17 g, 204 mmol) were combined in a solution of 1,4-dioxane (48 mL) and water (8 mL). Dimethylsulphate (17 mL, 178 mmol) was slowly added and the reaction was heated to 80-90° C. for 2 hours. The reaction was cooled to RT, water was added, and the aqueous phase extracted three times with EtOAc (200 mL). The organic phases were combined, dried with MgSO4, and filtered to give a red oil. The oil was purified by silica gel chromatography (10% EtOAc/Hexanes, Rf˜0.1) to give a white solid (3.59 g, 54.5% yield over three steps). ESI-MS (M+H)+ m/z calcd 259.1, found 259.0.

Workup

temperatureThe reaction was cooled to RT
extractionthe aqueous phase extracted three times with EtOAc (200 mL)
dry with materialdried with MgSO4
filtrationfiltered
customto give a red oil
customThe oil was purified by silica gel chromatography (10% EtOAc/Hexanes, Rf˜0.1)
customto give a white solid (3.59 g, 54.5% yield over three steps)

Sources & evidence

ORD record: ord-f29376032c714dd6a57c82decc13345b
Source dataset: uspto-grants-2014_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08642604B2

Reaction notes

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