Acetic Acid → 2-(Methoxy(4-nitrophenyl)methylene)malononitrile

HRID 870988Notes

Reaction equation

HRID 870988 reaction equation
[OH:1][C:2]([C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][CH:9]=1)=[C:3]([C:6]#[N:7])[C:4]#[N:5].[CH3:17][Si](C=[N+]=[N-])(C)C.C(O)(=O)C>C(#N)C.CO.C(OCC)C.CCOC(C)=O>[CH3:17][O:1][C:2]([C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][CH:9]=1)=[C:3]([C:4]#[N:5])[C:6]#[N:7]

Participants

8

Reactant 3

HCID 176Acetic AcidHCID 167693TrimethylsilyldiazomethaneHCID 858427932-[Hydroxy(4-nitrophenyl)methylene]malononitrile

Product 1

HCID 128622622-(Methoxy(4-nitrophenyl)methylene)malononitrile

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

3-Hydroxy-3-(4-nitrophenyl)-2-cyanoacrylonitrile (21.5 g, 0.10 mol) was dissolved in acetonitrile (430 mL) and of methanol (43 mL) in a flask equipped with a dropping funnel, a thermometer, a stir bar, and argon atmosphere. The flask was immersed in a −15° C. bath to the level that the internal temperature was maintained between −5° C. and 0° C. (75 mL of a 2.0 M solution in diethyl ether, 0.15 mol) was added dropwise over 20 min. HPLC analysis showed incomplete reaction, and an additional portion (25 mL, 0.05 mol) of trimethylsilyldiazomethane solution was added. This was repeated with 35 mL (0.07 mol). After 20 min, the mixture was poured into a rapidly-stirred solution of acetic acid (15 g, 0.25 mol) in EtOAc (1.8 L). The mixture was extracted with water (3×1.5 L), filtered through phase separation paper, and concentrated in vacuo. the solid residue weighed 14.4 g and was used in the next step without further purification. NMR (60 MHz) (CDCl3) δ 8.0 (AB, 4H); 4.0 (s, 3H).

Workup

  1. customequipped with a dropping funnel
  2. customwas immersed in a −15° C.
  3. additionwas added dropwise over 20 min
  4. customreaction
  5. extractionThe mixture was extracted with water (3×1.5 L)
  6. filtrationfiltered through phase separation paper
  7. concentrationconcentrated in vacuo
  8. customwas used in the next step without further purification

Sources & evidence

ORD record
ord-5756305685d74e369efceaa579128456
Source dataset
uspto-grants-2015_03
Patent number
US08969583B2

Reaction notes

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