Dimethylformamide → HCID 69204370, compound

HRID 2378328Notes

Reaction equation

HRID 2378328 reaction equation
N[C:2]1[CH:3]=[C:4]([C:10]([C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[C:16]([O:22][CH2:23][CH3:24])[CH:15]=2)=[CH:11][C:12]#[N:13])[CH:5]=[CH:6][C:7]=1OC.[C:25]([O-:28])([O-])=O.[Cs+].[Cs+].Cl[C:32]([O:34][CH3:35])=[O:33].C[N:37](C=O)C>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[CH3:35][O:34][C:32](=[O:33])[NH:37][C:7]1[CH:6]=[CH:5][C:4](/[C:10](/[C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[C:16]([O:22][CH2:23][CH3:24])[CH:15]=2)=[CH:11]/[C:12]#[N:13])=[CH:3][C:2]=1[O:28][CH3:25]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 6586Methyl chloroformateHCID 10796Cesium carbonateHCID 69204282HCID 69204282, compound

Product 1

HCID 69204370HCID 69204370, compoundYield 55%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred solution of 3-(3-amino-4-methoxy-phenyl)-3-(3-ethoxy-4-methoxy-phenyl)-acrylonitrile (0.20 g, 0.62 mmol) under a nitrogen atmosphere in anhydrous DMF (5 mL) was added Cs2CO3 (0.61 g, 1.86 mmol) and tetrabutylammonium iodide (0.69 g, 1.86 mmol). The mixture was stirred at ambient temperature for 30 minutes. Methyl chloroformate (0.14 mL, 1.86 mmol) was added dropwise into the suspension. The reaction mixture was stirred overnight under a nitrogen atmosphere. After this time, the reaction was diluted with ethyl acetate (50 mL). The solution was washed with water (2×50 mL), sodium carbonate (aq, 50 mL), and then brine (50 mL). The organic layer was dried over sodium sulfate, filtered, and then concentrated. The crude product was purified by silica gel chromatography (1:4:5, EtOAc: CH2Cl2: hexanes) followed by tituration with diethyl ether to afford (Z)-{4-[2-cyano-1-(3-ethoxy-4-methoxy-phenyl)-vinyl]-2-methoxy-phenyl}-carbamic acid methyl ester as a white solid (0.13 g, 55% yield): mp: 148-149° C. 1H NMR (400M Hz, CDCl3) δ 8.20 (s, 1H), 7.23 (s, 1H), 7.00 (m, 2H), 6.90 (d, 1H, J=8.4 Hz), 6.87 (d, 1H, J=2.0 Hz), 6.81 (d, 1H, J=8.4 Hz), 5.59 (s, 1H), 4.10 (q, 2H, J=6.8 Hz), 3.92(s, 3H), 3.91 (s, 3H), 3.78 (s, 3H), 1.45 (t, 3H, J=6.8 Hz). Anal. Calcd for C21H22N2O5: C, 65.96; H, 5.80; N, 7.33. Found: C, 65.99; H, 6.05; N, 7.10.

Workup

  1. stirringThe reaction mixture was stirred overnight under a nitrogen atmosphere
  2. washThe solution was washed with water (2×50 mL), sodium carbonate (aq, 50 mL)
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude product was purified by silica gel chromatography (1:4:5, EtOAc: CH2Cl2: hexanes)

Sources & evidence

ORD record
ord-53c2aeedd9cf4509bd2b8a4afc9f7217
Source dataset
uspto-grants-2008_12
Patent number
US07470723B2

Reaction notes

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